CN115779969A - Catalyst for mercaptan conversion in gasoline and preparation method thereof - Google Patents
Catalyst for mercaptan conversion in gasoline and preparation method thereof Download PDFInfo
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- CN115779969A CN115779969A CN202211562570.0A CN202211562570A CN115779969A CN 115779969 A CN115779969 A CN 115779969A CN 202211562570 A CN202211562570 A CN 202211562570A CN 115779969 A CN115779969 A CN 115779969A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 84
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 title description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 329
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 107
- 239000011148 porous material Substances 0.000 claims abstract description 25
- SSSYTNQOUFVWCO-UHFFFAOYSA-N [Co](C#N)C#N.[Ti] Chemical class [Co](C#N)C#N.[Ti] SSSYTNQOUFVWCO-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 95
- 238000010521 absorption reaction Methods 0.000 claims description 49
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 42
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 42
- 239000008367 deionised water Substances 0.000 claims description 42
- 229910021641 deionized water Inorganic materials 0.000 claims description 42
- 238000001035 drying Methods 0.000 claims description 33
- 239000000243 solution Substances 0.000 claims description 32
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 26
- MPMSMUBQXQALQI-UHFFFAOYSA-N cobalt phthalocyanine Chemical class [Co+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 MPMSMUBQXQALQI-UHFFFAOYSA-N 0.000 claims description 19
- 238000005507 spraying Methods 0.000 claims description 17
- 239000007864 aqueous solution Substances 0.000 claims description 16
- 230000004913 activation Effects 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 11
- 239000012298 atmosphere Substances 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 5
- 230000003213 activating effect Effects 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 2
- IDUKLYIMDYXQQA-UHFFFAOYSA-N cobalt cyanide Chemical compound [Co].N#[C-] IDUKLYIMDYXQQA-UHFFFAOYSA-N 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 claims 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims 1
- 150000003608 titanium Chemical class 0.000 claims 1
- 239000000428 dust Substances 0.000 abstract description 5
- 238000007667 floating Methods 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 230000009471 action Effects 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 12
- 238000001179 sorption measurement Methods 0.000 description 11
- 238000005470 impregnation Methods 0.000 description 8
- 230000008569 process Effects 0.000 description 7
- 238000005303 weighing Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 238000012360 testing method Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- PMBXCGGQNSVESQ-UHFFFAOYSA-N 1-Hexanethiol Chemical compound CCCCCCS PMBXCGGQNSVESQ-UHFFFAOYSA-N 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000003513 alkali Substances 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 238000004523 catalytic cracking Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- 238000007605 air drying Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000009969 flowable effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
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Abstract
The invention relates to the technical field of catalysts, in particular to a catalyst for converting mercaptan in gasoline and a preparation method thereof. The carrier of the catalyst for converting the mercaptan in the gasoline is activated active carbon, the active component comprises sulfonated titanium-cobalt cyanide, and the auxiliary active component comprises potassium hydroxide and Fe 2 O 3 . The activated carbon can remove floating dust on the surface of the activated carbon and in the pore channels, the pore channels are more developed, the surface is cleaner, so that the active components can enter the pore channels, the active components are more uniformly distributed, and the active components are more easily combined with the surface of the activated carbon. Activated carbon matched with active component sulfonated titanium cobalt cyanide and auxiliary active componentPotassium hydroxide and Fe 2 O 3 Under the combined action, the finally obtained catalyst for converting the mercaptan in the gasoline has the advantages of high catalytic activity, good stability, mild use conditions and the like, and the environmental protection problem caused by the mercaptan removal of the gasoline is effectively reduced.
Description
Technical Field
The invention relates to the technical field of catalysts, in particular to a catalyst for converting mercaptan in gasoline and a preparation method thereof.
Background
Along with the improvement of gasoline standards in China, an oil refining process is continuously improved and optimized, the quality of catalytic cracking gasoline is usually improved through selective hydrodesulfurization, but the problem of mercaptan content increase is often caused, and mercaptan is not easy to decompose, so that doctor tests of the catalytic cracking gasoline are unqualified, and the use of the gasoline is influenced.
The traditional alkali liquor sweetening process generates a large amount of alkali residues, which brings environmental protection problems, and the fixed bed gasoline sweetening process has the characteristics of good environmental protection and high mercaptan conversion rate, and is widely applied to the post-treatment of oil products. The core of the fixed bed gasoline sweetening process is a mercaptan conversion catalyst.
Chinese patent CN104841484A discloses a preparation method of a mercaptan conversion catalyst in gasoline, in which a certain amount of organic solvent is required, and therefore, volatilization of organic compounds is inevitably generated during the catalyst preparation process, resulting in excessive material consumption and environmental pollution. In addition, in order to better dissolve and uniformly impregnate the active component, the preparation method also needs to use ultrasonic treatment, the carrier active carbon is broken in the ultrasonic treatment process, a certain amount of carbon powder is generated, not only the carrier is lost, but also the active component is lost, and the manufacturing cost of the catalyst is increased.
Chinese patent CN101590408A discloses a mercaptan conversion catalyst and a preparation method thereof, the catalyst is improved by the patent, the sulfur capacity of the catalyst is improved, the service life of the catalyst is prolonged, but the size of the sulfur capacity still limits the long-term use of the catalyst. In addition, the catalyst of the patent uses DMF in the preparation process, and since DMF is an organic substance, the catalyst may cause loss of active components of the catalyst due to DMF loss when used for mercaptan removal in gasoline with complex components, and thus, as described in the patent, the catalyst is suitable for gas mercaptan removal.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide a catalyst for converting mercaptan in gasoline and a preparation method thereof, wherein the catalyst for converting mercaptan in gasoline has high activity and excellent stability.
The invention provides a catalyst for converting mercaptan in gasoline, wherein the carrier of the catalyst is activated carbon, the active component comprises sulfonated titanium cobalt cyanide, and the auxiliary active component comprises potassium hydroxide and Fe 2 O 3 。
Preferably, in the catalyst, the mass content of the sulfonated titanium cobalt cyanide is 0.3-1.0%, the mass content of the potassium hydroxide is 9-12%, and the mass content of the Fe 2 O 3 The mass content of (A) is 0.05% -0.5%.
Preferably, the activated carbon is prepared by the following method:
mixing the activated carbon with water, carrying out activation treatment at 95-105 ℃, and drying to obtain activated carbon.
Preferably, the activated carbon is cylindrical activated carbon, the diameter of the activated carbon is 3-7 mm, the water absorption rate is not less than 35%, the average pore diameter is 2.5-6 nm, and the specific surface area is not less than 180m 2 (ii)/g, carbon content not less than 80%.
Preferably, the time of the activation treatment is 3 to 4 hours;
the drying temperature is 120-180 ℃.
The invention also provides a preparation method of the catalyst for converting the mercaptan in the gasoline, which comprises the following steps:
a) Uniformly spraying ferric nitrate solution on activated carbon, standing and adsorbing for 1-6 h at normal temperature, and treating for 2-6 h at 440-460 ℃ under inert atmosphere;
b) Uniformly spraying an ammonia water solution of sulfonated cobalt phthalocyanine on the activated carbon treated in the step A), standing and adsorbing for 1-6 h at normal temperature, and drying at 120-180 ℃;
c) And B), uniformly spraying a potassium hydroxide aqueous solution on the activated carbon treated in the step B), standing at normal temperature for adsorption for 1-6 h, activating at 60-80 ℃ for 6-8 h, and drying at 120-180 ℃ to obtain the catalyst for converting the mercaptan in the gasoline.
Preferably, in the step a), the solvent of the ferric nitrate solution is deionized water;
the mass of the deionized water in the ferric nitrate solution is 0.9-1.1 times of the water absorption capacity of the activated carbon.
Preferably, in step a), the gas forming the inert atmosphere comprises one or more of nitrogen, helium and argon.
Preferably, in the step B), the solvent in the ammonia water solution of the sulfonated cobalt phthalocyanine is ammonia water;
the mass of the ammonia water in the ammonia water solution of the sulfonated cobalt phthalocyanine is 0.9 to 1.1 times of the water absorption capacity of the activated carbon treated in the step A).
Preferably, in the step C), the solvent in the potassium hydroxide aqueous solution is deionized water;
the mass of the deionized water in the potassium hydroxide aqueous solution is 0.9 to 1.1 times of the water absorption capacity of the activated carbon treated in the step B).
The invention provides a catalyst for converting mercaptan in gasoline, wherein the carrier of the catalyst is activated carbon, the active component comprises sulfonated titanium cobalt cyanide, and the auxiliary active component comprises potassium hydroxide and Fe 2 O 3 . The activated carbon can remove floating dust on the surface of the activated carbon and in the pore channels, the pore channels are more developed, the surface is cleaner, so that the active components can enter the pore channels, the active components are more uniformly distributed, and the active components are more easily combined with the surface of the activated carbon. Activated carbon matched with active component sulfonated titanium cobalt cyanide and auxiliary active components potassium hydroxide and Fe 2 O 3 Under the combined action, the finally obtained catalyst for converting the mercaptan in the gasoline has high catalytic activity, good stability and use stripsThe method has the advantages of mild components and the like, and effectively reduces the environmental protection problem caused by gasoline sweetening.
Detailed Description
The technical solutions of the present invention will be described clearly and completely below with reference to embodiments of the present invention, and it should be apparent that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
The invention provides a catalyst for converting mercaptan in gasoline, wherein the carrier of the catalyst is activated carbon, the active component comprises sulfonated titanium cobalt cyanide, and the auxiliary active component comprises potassium hydroxide and Fe 2 O 3 。
In some embodiments of the invention, in the catalyst, the mass content of the sulfonated titanium cobalt cyanide is 0.3-1.0%, the mass content of the potassium hydroxide is 9-12%, and the mass content of the Fe 2 O 3 The mass content of the active carbon is 0.05-0.5 percent, and the rest is activated active carbon.
In certain embodiments, the catalyst comprises 0.3% by mass of sulfonated titanium cobalt cyanide, 9.5% by mass of potassium hydroxide, and Fe 2 O 3 The mass content of (A) is 0.1%, and the mass content of activated carbon is 90.1%.
In certain embodiments of the present invention, the activated carbon is prepared according to the following method:
mixing the activated carbon with water, carrying out activation treatment at 95-105 ℃, and drying to obtain activated carbon.
The active carbon is cylindrical active carbon, the diameter is 3-7 mm, the water absorption rate is not less than 35 percent (by mass percent), the average pore diameter is 2.5-6 nm, and the specific surface area is not less than 180m 2 The carbon content is not less than 80% (by mass percent). In certain embodiments of the invention, the activated carbon has a diameter of 3.7 to 4.2mm or 3.6 to 4.1mm and a water absorption of 46% or 115% (by mass); the average pore diameter is 3.94nm or 3.47nm; ratio ofSurface area 341m 2 G or 620m 2 (ii)/g; the carbon content was 89.36% or 92.80% (by mass). The invention further limits the indexes of the activated carbon, on one hand, the method is beneficial to the uniform impregnation of the active components in the impregnation process, on the other hand, the method is beneficial to the entrance and exit of macromolecular (more than C6) mercaptan into and out of the catalyst pore canal, and is more beneficial to the conversion of the macromolecular mercaptan.
The water may be deionized water.
The mass of the deionized water is 1-2 times of the water absorption capacity of the activated carbon; specifically, the ratio may be 1.5 times.
The activation treatment time is 3-4 h; specifically, it may be 3.5 hours.
After the activation treatment, the method further comprises the following steps: washing with deionized water. The number of flushes may be 2.
The activated carbon can remove floating dust on the surface of the activated carbon and in the pore channels, the pore channels are developed, the surface is cleaner, so that the active components can enter the pore channels, the active components are distributed more uniformly and are combined with the surface of the activated carbon more easily. If the activated treatment is not carried out, floating dust can block the pore channels and adhere to the surface of the activated carbon, active components are difficult to enter the pore channels of the activated carbon in the impregnation process, and the active components can be combined with the floating dust on the surface of the activated carbon to cause uneven impregnation and loss or loss of the active components.
In some embodiments of the present invention, the drying temperature is 120 to 180 ℃, and specifically, may be 120 ℃; the time is 10 to 12 hours, and specifically 11 hours. The drying is carried out in a forced air drying cabinet.
In certain embodiments of the present invention, the activated carbon has a water absorption of 47% to 119% (by mass); specifically, it may be 52% or 119%.
In certain embodiments of the invention, the thiol may be hexanethiol.
In certain embodiments of the invention, the catalyst has an average pore diameter of 3.37 to 3.94nm; specifically, it may be 3.75nm or 3.37nm.
The catalyst provided by the invention is suitable for converting any one-component mercaptan or mixed-component mercaptan in C1-C10.
The invention also provides a preparation method of the catalyst for converting the mercaptan in the gasoline, which comprises the following steps:
a) Uniformly spraying ferric nitrate solution on activated carbon, standing and adsorbing for 1-6 h at normal temperature, and treating for 2-6 h at 450 ℃ in an inert atmosphere;
b) Uniformly spraying an ammonia water solution of sulfonated cobalt phthalocyanine on the activated carbon treated in the step A), standing and adsorbing for 1-6 h at normal temperature, and drying at 120-180 ℃;
c) And B), uniformly spraying a potassium hydroxide aqueous solution on the activated carbon treated in the step B), standing at normal temperature for adsorption for 1-6 h, activating at 60-80 ℃ for 6-8 h, and drying at 120-180 ℃ to obtain the catalyst for converting the mercaptan in the gasoline.
In step A):
uniformly spraying the ferric nitrate solution on the activated carbon, standing and adsorbing for 1-6 h at normal temperature, and treating for 2-6 h at 440-460 ℃ under inert atmosphere.
In some embodiments of the present invention, the solvent of the ferric nitrate solution is deionized water, and the solute may be Fe (NO) 3 ) 3 ·9H 2 O。
In some embodiments of the invention, the mass of the deionized water in the ferric nitrate solution is 0.9-1.1 times of the water absorption capacity of the activated carbon; specifically, the ratio may be 1.05 times.
In certain embodiments of the invention, the adsorption is performed at ambient temperature for 2 hours.
In certain embodiments of the present invention, the inert atmosphere forming gas comprises one or more of nitrogen, helium, and argon; preferably nitrogen. Preferably, the gas forming the inert atmosphere is flowable, and is capable of being discharged while being charged, for discharging oxynitride gas generated by decomposition of ferric nitrate from the system.
In certain embodiments of the invention, the temperature of the treatment under an inert atmosphere is 450 ℃ for 3h.
In some embodiments of the present invention, after the treatment for 2 to 6 hours at 440 to 460 ℃ under the inert atmosphere, the method further comprises: naturally cooling to room temperature.
In certain embodiments of the present invention, the water absorption of the activated carbon treated in step a) is 46% to 120% (by mass); specifically, it may be 52.5% or 120%.
In step B):
uniformly spraying an ammonia water solution of sulfonated cobalt phthalocyanine on the activated carbon treated in the step A), standing and adsorbing for 1-6 h at normal temperature, and drying at 120-180 ℃.
In some embodiments of the present invention, the solvent in the aqueous ammonia solution of sulfonated cobalt phthalocyanine is aqueous ammonia, and the mass concentration of the aqueous ammonia is 20% to 30%, and specifically, may be 25%.
In the invention, the solvent in the ammonia water solution of the sulfonated cobalt phthalocyanine is ammonia water, and the solvent does not contain an active component dispersing agent and DMF, so that new impurities can be avoided from being introduced.
In some embodiments of the invention, the mass of the ammonia water in the ammonia water solution of the sulfonated cobalt phthalocyanine is 0.9 to 1.1 times of the water absorption capacity of the activated carbon treated in the step A); specifically, the ratio may be 1.05 times.
In certain embodiments of the invention, the adsorption is performed at ambient temperature for 2 hours.
In certain embodiments of the present invention, the temperature of the drying is 120 ℃; the time is 6 to 24 hours, and specifically, can be 12 hours.
In certain embodiments of the present invention, the water absorption of the activated carbon treated in step B) is 51% to 119% (by mass); specifically, it may be 51% or 118.1%.
In step C):
and B), uniformly spraying a potassium hydroxide aqueous solution on the activated carbon treated in the step B), standing at normal temperature for adsorption for 1-6 h, activating at 60-80 ℃ for 6-8 h, and drying at 120-180 ℃ to obtain the catalyst for converting the mercaptan in the gasoline.
In certain embodiments of the invention, the solvent in the aqueous potassium hydroxide solution is deionized water.
In some embodiments of the invention, the mass of the deionized water in the potassium hydroxide aqueous solution is 0.9-1.1 times of the water absorption capacity of the activated carbon treated in the step B); specifically, the ratio may be 1.05 times.
In certain embodiments of the invention, the adsorption is allowed to stand at ambient temperature for 1 hour.
In certain embodiments of the invention, the activation temperature is 60 ℃ and the time is 6 hours.
In certain embodiments of the present invention, the temperature of the drying is 120 ℃; the time is 6 to 24 hours, and specifically, can be 12 hours.
In the preparation method of the catalyst for converting the mercaptan in the gasoline, the nearly isovolumetric impregnation method is adopted for adsorption, compared with the excess impregnation method, the nearly isovolumetric impregnation method does not need to remove redundant impregnation liquid, the operation method is simple and convenient, and the distribution of active components is relatively uniform.
The source of the above-mentioned raw materials is not particularly limited, and the raw materials may be generally commercially available.
In order to further illustrate the present invention, the following will describe in detail a catalyst for converting mercaptan in gasoline and a method for preparing the same according to the present invention with reference to the following examples, which should not be construed as limiting the scope of the present invention.
The activated carbon used in the examples is generally commercially available.
Example 1
The activated carbon used is designated as activated carbon A1.
1) Preparing activated carbon: weighing activated carbon, putting the activated carbon into a beaker, adding deionized water (the mass of the deionized water is 1.5 times of the water absorption capacity of the activated carbon), performing activation treatment for 3.5h at 100 ℃, washing the activated carbon for 2 times by using the deionized water, putting the activated carbon into an air-blowing drying oven for drying, drying the activated carbon for 11h at 120 ℃, and detecting that the water absorption of the activated carbon is 52% (in mass percentage);
2) Weighing 230g of activated carbon activated in the step 1) and Fe (NO) 3 ) 3 ·9H 2 O1.292 g and deionized water (the mass of the deionized water is 1.05 times of the water absorption capacity of the activated carbon), and the weighed Fe (NO) is added 3 ) 3 ·9H 2 Dissolving O in deionized water to prepare ferric nitrate solution, uniformly spraying the ferric nitrate solution on the activated carbon, standing and adsorbing for 2h at normal temperature, treating for 3h at 450 ℃ in a nitrogen atmosphere, naturally cooling to room temperature, and detecting that the water absorption of the activated carbon treated in the step 2) is 52.5% (by mass percentage);
3) Weighing 199.336g of the activated carbon treated in the step 2), 0.663g of sulfonated titanium cobalt cyanide and 1.05 times of the water absorption capacity of the activated carbon treated in the step 2 by mass of ammonia water; the mass concentration of ammonia water is 25 percent), dissolving sulfonated cobalt phthalocyanine in the ammonia water to prepare an ammonia water solution of the sulfonated cobalt phthalocyanine, uniformly spraying the ammonia water solution on the activated carbon treated in the step 2), standing and adsorbing at normal temperature for 2 hours, and drying at 120 ℃ for 12 hours; detecting that the water absorption of the activated carbon treated in the step 3) is 51% (by mass percentage);
4) 135.75g of the activated carbon treated in the step 3), 14.25g of potassium hydroxide and deionized water (the mass of the deionized water is 1.05 times of the water absorption capacity of the activated carbon treated in the step 3) are weighed, the weighed potassium hydroxide is dissolved in the deionized water to prepare a potassium hydroxide aqueous solution, the potassium hydroxide aqueous solution is uniformly sprayed on the activated carbon treated in the step 3), the activated carbon is kept stand at normal temperature for adsorption for 1h, then the activated carbon is activated for 6h at 60 ℃, and finally the activated carbon is dried for 12h at 120 ℃. The prepared catalyst sample is marked as # 1, and the average pore diameter of the catalyst is 3.75nm.
Example 2
The difference from example 1 is that:
the activated carbon used is designated activated carbon A2.
The preparation steps and parameters are the same as those of the example 1, wherein the water absorption of the activated carbon obtained in the step 1) is 119% (by mass percentage); the water absorption of the activated carbon treated in the step 2) is 120% (by mass percentage); the water absorption of the activated carbon treated in the step 3) is 118.1% (by mass percentage); the prepared catalyst sample is marked as # 2, and the average pore diameter of the catalyst is 3.37nm.
Comparative example 1
The difference from example 1 is that:
the activated carbon used is designated as activated carbon B1.
The preparation steps and parameters are the same as those of example 1, wherein the water absorption of the activated carbon obtained in the step 1) is 57% (by mass); the water absorption of the activated carbon treated in the step 2) is 58% (by mass percentage); the water absorption of the activated carbon treated in the step 3) is 56.7% (by mass percentage); the prepared catalyst sample is marked as # 3, and the average pore diameter of the catalyst is 1.75nm.
Comparative example 2
The difference from example 1 is that:
the activated carbon used is designated as activated carbon B1.
1) Preparing activated carbon: weighing activated carbon, putting the activated carbon into a beaker, adding deionized water (the mass of the deionized water is 1.5 times of the water absorption capacity of the activated carbon), performing activation treatment for 3.5h at 100 ℃, washing for 2 times by using the deionized water, putting the activated carbon into an air-blast drying oven for drying, drying for 11h at 120 ℃, and detecting that the water absorption of the activated carbon is 57% (by mass percent);
2) Weighing 199.668g of activated carbon in the step 1), 0.332g of sulfonated titanium cobalt cyanide and ammonia water (the mass of the ammonia water is 1.05 times of the water absorption amount of the activated carbon in the step 1); the mass concentration of ammonia water is 25 percent), dissolving sulfonated cobalt phthalocyanine in the ammonia water to prepare an ammonia water solution of the sulfonated cobalt phthalocyanine, uniformly spraying the ammonia water solution on the activated carbon in the step 1), standing and adsorbing at normal temperature for 2 hours, and drying at 120 ℃ for 12 hours; detecting that the water absorption of the activated carbon treated in the step 2) is 56% (by mass percentage);
3) 135.75g of the activated carbon treated in the step 2), 14.25g of potassium hydroxide and deionized water (the mass of the deionized water is 1.05 times of the water absorption capacity of the activated carbon treated in the step 2) are weighed, the weighed potassium hydroxide is dissolved in the deionized water to prepare a potassium hydroxide aqueous solution, the potassium hydroxide aqueous solution is uniformly sprayed on the activated carbon treated in the step 2), the activated carbon is kept stand at normal temperature for adsorption for 1h, then the activated carbon is activated for 6h at 60 ℃, and finally the activated carbon is dried for 12h at 120 ℃. The prepared catalyst sample is labeled 4#, and the average pore diameter of the catalyst is 1.79nm.
Comparative example 3
The difference from example 1 is that:
the activated carbon used is designated as activated carbon B1.
1) Preparing activated carbon: weighing activated carbon, putting the activated carbon into a beaker, adding deionized water (the mass of the deionized water is 1.5 times of the water absorption capacity of the activated carbon), performing activation treatment for 3.5h at 100 ℃, washing the activated carbon for 2 times by using the deionized water, putting the activated carbon into an air-blast drying oven for drying, drying the activated carbon for 11h at 120 ℃, and detecting that the water absorption of the activated carbon is 57% (in mass percentage);
2) 199.37g of activated carbon in the step 1), 0.63g of sulfonated titanium cobalt cyanide and 1.05 times of water absorption capacity of ammonia water (the mass of the ammonia water is 1.05 times of that of the activated carbon in the step 1) are weighed; the mass concentration of ammonia water is 25 percent), dissolving sulfonated cobalt phthalocyanine in the ammonia water to prepare an ammonia water solution of the sulfonated cobalt phthalocyanine, uniformly spraying the ammonia water solution on the activated carbon in the step 1), standing and adsorbing at normal temperature for 2 hours, and drying at 120 ℃ for 12 hours; detecting that the water absorption of the activated carbon treated in the step 2) is 56% (by mass percentage);
3) 135.75g of the activated carbon treated in the step 2), 7.1g of potassium hydroxide and deionized water (the mass of the deionized water is 1.05 times of the water absorption capacity of the activated carbon treated in the step 2) are weighed, the weighed potassium hydroxide is dissolved in the deionized water to prepare a potassium hydroxide aqueous solution, the potassium hydroxide aqueous solution is uniformly sprayed on the activated carbon treated in the step 2), the activated carbon is kept stand at normal temperature for adsorption for 1h, then the activated carbon is activated for 6h at 60 ℃, and finally the activated carbon is dried for 12h at 120 ℃. The prepared catalyst sample is marked as # 5, and the average pore diameter of the catalyst is 1.81nm.
Comparative example 4
The difference from example 1 is that:
the activated carbon used is designated as activated carbon B2.
The preparation steps and parameters are the same as those of the example 1, wherein the water absorption of the activated carbon obtained in the step 1) is 78% (by mass percentage); the water absorption of the activated carbon treated in the step 2) is 79.3% (by mass percentage); the water absorption of the activated carbon treated in the step 3) is 77.6% (by mass); the prepared catalyst sample is marked as No. 6, and the average pore diameter of the catalyst is 1.80nm.
Comparative example 5
The difference from example 1 is that:
the activated carbon used is designated as activated carbon A1.
1) Preparing activated carbon: weighing activated carbon, putting the activated carbon into a beaker, adding deionized water (the mass of the deionized water is 1.5 times of the water absorption capacity of the activated carbon), performing activation treatment for 3.5h at 100 ℃, washing the activated carbon for 2 times by using the deionized water, putting the activated carbon into an air-blowing drying oven for drying, drying the activated carbon for 11h at 120 ℃, and detecting that the water absorption of the activated carbon is 52% (in mass percentage);
2) 199.336g of activated carbon activated in the step 1), 0.663g of sulfonated titanium cobalt cyanide and ammonia water (the mass of the ammonia water is 1.05 times of the water absorption capacity of the activated carbon activated in the step 1) are weighed; the mass concentration of ammonia water is 25 percent), dissolving sulfonated cobalt phthalocyanine in the ammonia water to prepare an ammonia water solution of the sulfonated cobalt phthalocyanine, uniformly spraying the ammonia water solution on the activated carbon in the step 1), standing and adsorbing at normal temperature for 2 hours, and drying at 120 ℃ for 12 hours; detecting that the water absorption of the activated carbon treated in the step 2) is 51.3% (by mass percentage);
3) 135.75g of the activated carbon treated in the step 2), 14.25g of potassium hydroxide and deionized water (the mass of the deionized water is 1.05 times of the water absorption capacity of the activated carbon treated in the step 2) are weighed, the weighed potassium hydroxide is dissolved in the deionized water to prepare a potassium hydroxide aqueous solution, the potassium hydroxide aqueous solution is uniformly sprayed on the activated carbon treated in the step 2), the activated carbon is kept stand at normal temperature for adsorption for 1h, then the activated carbon is activated for 6h at 60 ℃, and finally the activated carbon is dried for 12h at 120 ℃. A sample of the prepared catalyst is labeled 7#, and the average pore diameter of the catalyst is 3.83nm.
Example 3
The mercaptan conversion evaluation experiment was carried out in a continuous fixed bed reactor using the above catalyst samples, respectively, and the experiment was as follows:
a reactor: a stainless steel tubular reactor with an inner diameter of 4.0cm and a length of 16cm;
catalyst: the catalyst samples 1# to 7#;
raw materials: hexane solution with hexanethiol as target and 40ppm mercaptan sulfur content
Evaluation conditions were as follows: the dosage of the catalyst is as follows: 150mL, liquid feed rate: the volume space velocity is 3.0h -1 Normal temperature and normal pressure.
The feeding mode is as follows: the hexane solution containing 40ppm of mercaptan sulfur was fed into the reaction system by a feed pump, and the catalyst activity evaluation experiment was carried out at normal temperature and pressure.
The judgment method of the activity and the stability of the catalyst comprises the following steps: and (4) carrying out doctor test analysis on the product, wherein the longest time for the catalyst to stably run is the standard under the condition that the doctor test analysis of the product is qualified.
The compositions of the catalyst samples of examples 1 to 2 and comparative examples 1 to 5 are shown in Table 1.
TABLE 1 Components and Mass contents of catalyst samples of examples 1 to 2 and comparative examples 1 to 5
The results of the physical index measurements of the activated carbon of examples 1 to 2 and comparative examples 1 to 5 are shown in table 2. Wherein the water absorption is calculated by mass percent, and the carbon content is calculated by mass percent.
Table 2 physical index test results of activated carbon of examples 1 to 2 and comparative examples 1 to 5
The results of activity measurement of the catalyst samples of examples 1 to 2 and comparative examples 1 to 5 are shown in table 3.
Table 3 results of activity test of catalyst samples of examples 1 to 2 and comparative examples 1 to 5
From the above detection results, it can be seen that: (1) the average pore diameter of the catalyst carrier active carbon is between 3 and 6nm, and the prepared mercaptan conversion catalyst has higher activity; (2) when the mass content of the active component sulfonated titanium cobalt cyanide is 0.3-1.0% and the mass content of the auxiliary active component potassium hydroxide is 9-12%, the mercaptan conversion catalyst can show higher catalytic activity; (3) the evaluation results of example 1 (catalyst sample # 1) and comparative example 5 (catalyst sample # 7) showed that the co-active component Fe was increased 2 O 3 And the stability of the catalyst is obviously improved, and the running time of the catalyst is obviously increased.
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. The catalyst for converting mercaptan in gasoline features that the carrier of the catalyst is activated active carbon, the active component includes sulfonated titanium, cobalt cyanide and co-active component includes potassium hydroxide and Fe 2 O 3 。
2. The catalyst according to claim 1, wherein the mass content of sulfonated titanium-cobalt cyanide in the catalyst is 0.3-1.0%, the mass content of potassium hydroxide is 9-12%, and Fe 2 O 3 The mass content of the compound is 0.05-0.5%.
3. The catalyst according to claim 1, wherein the activated carbon is prepared by the following method:
mixing the activated carbon with water, carrying out activation treatment at 95-105 ℃, and drying to obtain activated carbon.
4. The catalyst according to claim 3, wherein the activated carbon is a cylindrical activated carbon having a diameter of 3 to 7mm, a water absorption of not less than 35%, an average pore diameter of 2.5 to 6nm, and a specific surface area of not less than 180m 2 (ii)/g, carbon content not less than 80%.
5. The catalyst according to claim 3, characterized in that the time of the activation treatment is between 3 and 4 hours;
the drying temperature is 120-180 ℃.
6. A preparation method of a catalyst for converting mercaptan in gasoline comprises the following steps:
a) Uniformly spraying a ferric nitrate solution on the activated carbon, standing and adsorbing for 1-6 h at normal temperature, and treating for 2-6 h at 440-460 ℃ under an inert atmosphere;
b) Uniformly spraying an ammonia water solution of sulfonated cobalt phthalocyanine on the activated carbon treated in the step A), standing and adsorbing at normal temperature for 1-6 h, and drying at 120-180 ℃;
c) And C), uniformly spraying a potassium hydroxide aqueous solution on the activated carbon treated in the step B), standing and adsorbing at normal temperature for 1-6 h, activating at 60-80 ℃ for 6-8 h, and drying at 120-180 ℃ to obtain the catalyst for converting the mercaptan in the gasoline.
7. The method according to claim 6, wherein in step A), the solvent of the ferric nitrate solution is deionized water;
the mass of the deionized water in the ferric nitrate solution is 0.9-1.1 times of the water absorption capacity of the activated carbon.
8. The method according to claim 6, wherein the gas forming the inert atmosphere in step A) comprises one or more of nitrogen, helium and argon.
9. The method according to claim 6, wherein in step B), the solvent in the aqueous ammonia solution of cobalt phthalocyanine sulfonate is aqueous ammonia;
the mass of the ammonia water in the ammonia water solution of the sulfonated cobalt phthalocyanine is 0.9 to 1.1 times of the water absorption capacity of the activated carbon treated in the step A).
10. The method according to claim 6, wherein in step C), the solvent in the aqueous potassium hydroxide solution is deionized water;
the mass of the deionized water in the potassium hydroxide aqueous solution is 0.9-1.1 times of the water absorption capacity of the activated carbon treated in the step B).
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