CN108404952B - Desulfurization catalyst with regular structure, preparation method thereof and sulfur-containing hydrocarbon desulfurization method - Google Patents
Desulfurization catalyst with regular structure, preparation method thereof and sulfur-containing hydrocarbon desulfurization method Download PDFInfo
- Publication number
- CN108404952B CN108404952B CN201710073752.4A CN201710073752A CN108404952B CN 108404952 B CN108404952 B CN 108404952B CN 201710073752 A CN201710073752 A CN 201710073752A CN 108404952 B CN108404952 B CN 108404952B
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- catalyst
- carrier
- transition metal
- regular structure
- desulfurization
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- 230000023556 desulfurization Effects 0.000 title claims abstract description 138
- 238000000034 method Methods 0.000 title claims abstract description 78
- 238000002360 preparation method Methods 0.000 title claims abstract description 67
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 64
- 239000011593 sulfur Substances 0.000 title claims abstract description 64
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 45
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 44
- 239000004215 Carbon black (E152) Substances 0.000 title claims abstract description 43
- 239000011159 matrix material Substances 0.000 claims abstract description 80
- 238000000576 coating method Methods 0.000 claims abstract description 76
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- 239000011248 coating agent Substances 0.000 claims abstract description 68
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 60
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- 239000000758 substrate Substances 0.000 claims abstract description 25
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/56—Foraminous structures having flow-through passages or channels, e.g. grids or three-dimensional monoliths
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
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Abstract
The invention discloses a desulfurization catalyst with a regular structure, a preparation method thereof and a desulfurization method for sulfur-containing hydrocarbon, wherein the catalyst comprises a regular structure carrier and an active component coating distributed on the inner surface and/or the outer surface of the regular structure carrier; the active component coating comprises 5-70 wt% of transition metal nitride and 30-95 wt% of matrix based on the total weight of the active component coating; the substrate contains 70-90 wt% of at least one metal oxide selected from IIA and IIB groups and 10-30 wt% of silicon oxide based on the total weight of the substrate. The catalyst has better desulfurization activity and desulfurization stability, and can improve the octane number of desulfurized oil products.
Description
Technical Field
The invention relates to the field of sulfur-containing hydrocarbon desulfurization, in particular to a desulfurization catalyst with a regular structure, a preparation method thereof and a sulfur-containing hydrocarbon desulfurization method.
Background
Sulfur in automotive fuels, after combustion, produces sulfur oxides. The material can inhibit the activity of a noble metal catalyst in an automobile exhaust converter, can cause irreversible poisoning, and can not realize the function of catalyzing and converting toxic gases in automobile exhaust, so that unburned non-methane hydrocarbon, nitrogen oxide and carbon monoxide are contained in the automobile exhaust. The emitted toxic gases are catalyzed by sunlight to easily form photochemical smog, and acid rain is caused. But also sulfur oxides themselves are one of the main causes of acid rain formation.
With the increasing emphasis on environmental protection, environmental regulations are becoming more stringent, and reducing the sulfur content in gasoline and diesel is considered to be one of the most important measures for improving air quality. Taking gasoline as an example, the european union specifies a sulfur content of less than 10 μ g/g in the euro V gasoline standard implemented in 2010. The current gasoline product standard GB 17930-2013 'automotive gasoline' in China requires that the sulfur content in the gasoline must be reduced to 10 mu g/g by 1 month and 1 day in 2018. But also the future gasoline quality standards will be more stringent.
The main method for desulfurization of fuel oil is hydrodesulfurization. However, as the fuel oil standard becomes stricter, the hydrogenation depth increases, and more severe reaction conditions such as higher reaction pressure and the like are required. In addition, for gasoline, since a large amount of olefins are contained, increasing the hydrogenation severity will lead to higher octane number loss, and therefore, some new desulfurization methods are continuously emerging, wherein the adsorption desulfurization is most concerned.
US7427581, US7182918, US6869522 and US6274533 disclose that the adsorbent is used for desulfurizing light sulfur-containing hydrocarbon under the hydrogen condition, and the adsorbent has the characteristics of high desulfurization depth, low hydrogen consumption, low octane number loss and the like, and can produce fuel oil with the sulfur content of below 30 mug/g. The adsorbent is prepared by using a mixture of zinc oxide, silica and alumina as a carrier, wherein the zinc oxide accounts for 10-90 wt%, the silica accounts for 5-85 wt%, and the alumina accounts for 5-30 wt%; the loaded active component is a reduced metal and can be at least one of cobalt, copper, manganese, tungsten, tin, nickel, iron, molybdenum, silver and vanadium. The adsorbent is used at 0.1-10.3 MPa, 37.7-537.7 ℃ and a weight hourly space velocity of 0.5-50 h-1And under the condition of hydrogen, capturing sulfur in the oil product on the adsorbent, hydrogenating and combining with zinc oxide, and simultaneously, due to the same hydrogenation effect of the transition metal on olefin, the octane number of the gasoline product is reduced. In order to compensate octane number loss caused by olefin reduction, the prior art generally adopts a method of promoting aromatization reaction and increasing aromatic hydrocarbon content,but inevitably results in increased benzene content in the gasoline. Furthermore, when the zinc oxide becomes saturated with bound sulfur, the desulfurization activity decreases, and sulfur must be removed by oxidative regeneration. In the frequent oxidation regeneration-reduction process, metals as active components can be aggregated, and the zinc oxide can be converted into zinc silicate and zinc aluminate in the regeneration process, so that the desulfurization activity of the adsorbent in the recycling process is reduced, the deactivation rate of the adsorbent is high, and the implementation effect of sulfur-containing hydrocarbon desulfurization is influenced.
It can be seen that, although deep desulfurization can be well achieved by adsorption desulfurization, the desulfurization activity and desulfurization stability still remain problems in practical applications. Therefore, there is a need to find new sorbents (also known as desulfurization catalysts) that overcome at least one of the above-mentioned drawbacks of the prior art.
Disclosure of Invention
The invention aims to provide a desulfurization catalyst with a regular structure, a preparation method thereof and a sulfur-containing hydrocarbon desulfurization method, so as to improve the desulfurization activity and the desulfurization stability of the catalyst and improve the octane number of a desulfurized oil product.
In order to achieve the above object, according to a first aspect of the present invention, there is provided a desulfurization catalyst of a structured structure comprising a structured carrier and an active component coating layer distributed on an inner surface and/or an outer surface of the structured carrier; the active component coating comprises 5-70 wt% of transition metal nitride and 30-95 wt% of matrix based on the total weight of the active component coating; the substrate contains 70-90 wt% of at least one metal oxide selected from IIA and IIB groups and 10-30 wt% of silicon oxide based on the total weight of the substrate.
According to a second aspect of the present invention, there is provided a method for preparing a desulfurization catalyst with a regular structure, comprising the steps of: s1, mixing a precursor of an oxide of at least one metal selected from IIA and IIB groups with a silicon oxide binder precursor to prepare a matrix coating slurry; s2, coating the substrate coating slurry on a regular structure carrier, drying and roasting to form the regular structure carrierForming a substrate coating on the inner surface and/or the outer surface to obtain a catalyst carrier; s3, contacting the catalyst supporter with a transition metal precursor solution, drying and roasting after the contact to form a transition metal oxide on the matrix coating to obtain a catalyst precursor; s4, adding the catalyst precursor into NH3/H2And carrying out reduction treatment in the atmosphere to reduce the transition metal oxide to form transition metal nitride, thereby obtaining the desulfurization catalyst with the regular structure.
According to a third aspect of the present invention, there is provided a desulfurization catalyst with a regular structure prepared by the preparation method of the present invention.
According to a fourth aspect of the present invention, there is provided a process for the desulfurization of sulfur-containing hydrocarbons, the process comprising: contacting a sulfur-containing hydrocarbon and a hydrogen donor with a catalyst; wherein the catalyst is the catalyst according to the invention.
By applying the desulfurization catalyst with the regular structure, the desulfurization activity and the desulfurization stability of the catalyst can be effectively improved, the content of benzene in a desulfurized oil product is reduced, the content of isomeric hydrocarbon is improved, and the octane number of the desulfurized oil product is improved; the desulfurization catalyst with the regular structure provided by the invention does not need frequent repeated regeneration, can be used for a long period, is not easy to lose and aggregate, improves the desulfurization stability, and reduces the unit consumption of the catalyst.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
In the present invention, the term "structured catalyst" is used to refer to a catalyst comprising a structured carrier and a coating of an active component distributed on the inner and/or outer surface of the carrier; the 'regular structure carrier' is a carrier with a regular structure; the regular structure reactor is a fixed bed reactor filled with a regular structure catalyst as a catalyst bed layer.
The invention provides a desulfurization catalyst with a regular structure, which comprises a regular structure carrier and an active component coating distributed on the inner surface (the surface of pores inside the carrier) and/or the outer surface of the regular structure carrier; the active component coating comprises 5-70 wt% of transition metal nitride and 30-95 wt% of matrix based on the total weight of the active component coating; the substrate contains 70-90 wt% of at least one metal oxide selected from IIA and IIB groups and 10-30 wt% of silicon oxide based on the total weight of the substrate.
The desulfurization catalyst of a regular structure according to the present invention is not particularly limited as long as it contains therein a transition metal nitride and a matrix having a specific component, and the amount of the active component coating layer distributed on the regular structure support by coating may be not particularly limited. Preferably, the content of the active component coating is 10-50 wt% based on the total weight of the regular structure catalyst; preferably 15 to 30 wt%.
According to the desulfurization catalyst with a regular structure, the active component coating preferably contains 5-70 wt% of transition metal nitride and 30-95 wt% of matrix based on the total weight of the active component coating; preferably, the active component coating layer contains 10 to 50 wt% of transition metal nitride and 50 to 90 wt% of matrix; particularly preferably, the active component coating layer contains 20-50 wt% of transition metal nitride and 50-80 wt% of matrix; it is particularly preferred that the active ingredient coating contains 30 to 50 wt% of the transition metal nitride and 50 to 70 wt% of the matrix.
According to the desulfurization catalyst with a regular structure of the present invention, the transition metal in the transition metal nitride is preferably selected from Sc (corresponding to nitride mainly ScN), Ti (corresponding to nitride mainly TiN), V (corresponding to nitride mainly VN), Fe (corresponding to nitride mainly Fe)3N, Co (the corresponding nitrides are mainly CoN)1.2) Ni (the corresponding nitride is mainly Ni)3N, Zr (the corresponding nitrides are mainly ZrN), Cr (the corresponding nitrides areThe corresponding nitride is mainly Cr2N, Mn (the corresponding nitride is mainly Mn)3N2) Cu (the corresponding nitride is mainly Cu)3N and Mo (the corresponding nitride is mainly Mo)2N) and W (the corresponding nitrides are mainly W2N), more preferably one or more selected from Co, Ni, Mo and W.
According to the desulfurization catalyst with a regular structure of the present invention, the oxide of at least one metal selected from the group consisting of group IIA and group IIB and the metal oxide having a sulfur storage property are contained in the matrix. Preferably, the oxide of at least one metal selected from the group consisting of group IIA and group IIB is an oxide of at least one metal selected from magnesium, zinc and calcium; preferably zinc oxide; preferably, the rare earth oxide is an oxide of lanthanum and/or cerium and/or neodymium, that is, the rare earth oxide is an oxide of at least one rare earth metal selected from lanthanum, cerium and neodymium.
The desulfurization catalyst with a regular structure according to the present invention, wherein the carrier with a regular structure can be used for a catalyst bed provided in a fixed bed reactor. The regular structure carrier can be a whole carrier block, a hollow pore channel structure is formed inside the regular structure carrier, a catalyst coating can be distributed on the inner wall of a pore channel, and the pore channel space can be used as a flowing space of fluid. Preferably, the structured support is selected from monolithic supports having a parallel cell structure with open ends. The regular structure carrier can be a honeycomb type regular carrier (honeycomb carrier for short) with honeycomb-shaped open pores on the cross section.
According to the desulfurization catalyst with a regular structure, the pore density of the cross section of the regular structure carrier is preferably 40-800 pores/square inch, preferably 100-400 pores/square inch, and the cross section area of each pore in the regular structure carrier is 400-1.8 × 105μm2Preferably 1500 to 22500 μm2The aperture ratio of the carrier surface of the regular structure carrier is 20-80%, preferably 50-80%. The shape of the hole may be one of square, regular triangle, regular hexagon, circle, and wave.
According to the desulfurization catalyst with a regular structure of the present invention, preferably, the carrier with a regular structure may be at least one selected from the group consisting of cordierite honeycomb carrier, mullite honeycomb carrier, diamond honeycomb carrier, corundum honeycomb carrier, zirconia corundum honeycomb carrier, quartz honeycomb carrier, nepheline honeycomb carrier, feldspar honeycomb carrier, alumina honeycomb carrier and metal alloy honeycomb carrier.
Meanwhile, the invention also provides a preparation method of the desulfurization catalyst with the regular structure, which comprises the following steps: s1, mixing a precursor of an oxide of at least one metal selected from IIA and IIB groups with a silicon oxide binder precursor to prepare a matrix coating slurry; s2, coating the slurry of the matrix coating on a regular structure carrier, drying and roasting to form a matrix coating on the inner surface and/or the outer surface of the regular structure carrier to obtain a catalyst carrier; s3, contacting the catalyst supporter with a transition metal precursor solution, drying and roasting after the contact to form a transition metal oxide on the substrate coating to obtain a catalyst precursor; s4, adding the catalyst precursor into NH3/H2And carrying out reduction treatment in the atmosphere to reduce the transition metal oxide to form transition metal nitride, thereby obtaining the desulfurization catalyst with the regular structure.
According to the production method of the present invention, preferably, the substrate coating slurry contains 70 to 90% by weight of a precursor of an oxide of at least one metal selected from groups IIA and IIB, as a metal oxide, and 10 to 30% by weight of a silica binder precursor, as silica, on a dry weight (dry weight) basis thereof.
According to the production method of the present invention, the matrix coating and the transition metal nitride formed on the structured carrier are collectively referred to as an active component coating. Preferably, the total content of the matrix coating layer and the transition metal nitride (i.e., the active component coating layer) is 10 to 50 wt%, preferably 15 to 30 wt%, and more preferably 20 to 30 wt%, based on the total weight of the structured desulfurization catalyst; preferably, the transition metal nitride is present in an amount of 5 to 70 wt% based on the total amount of the base coating layer and the transition metal nitride (i.e., the active component coating layer), and the base coating layer is present in an amount of 30 to 95 wt%; preferably, the content of the transition metal nitride is 10-50 wt%, and the content of the matrix coating is 50-90 wt%; preferably, the active component coating layer contains 20 to 50 wt% of transition metal nitride and 50 to 80 wt% of matrix; more preferably, the active ingredient coating layer contains 30 to 50 wt% of transition metal nitride and 50 to 70 wt% of matrix.
According to the preparation method of the invention, no special requirement is required on the solid content of the substrate coating slurry prepared in S1, however, the difficulty of coating the slurry can be increased due to the fact that the solid content of the slurry is too high, and the adhesion amount of each coating can be reduced due to the fact that the solid content of the slurry is too low, so that the coating times are increased. Preferably, the solid content of the substrate coating slurry in S1 is 10-45 wt%, preferably 20-40 wt%.
According to the preparation method of the present invention, preferably, in S1, a precursor of an oxide of at least one metal selected from groups IIA and IIB and a solution are mixed and ground to obtain a grinding slurry; and then adding the silicon oxide binder precursor into the grinding solution to prepare matrix coating slurry. Among them, the solid content of the grinding slurry is preferably 15 to 60% by weight, preferably 25 to 40% by weight; the solution is deionized water.
The production method according to the present invention, wherein the oxide of at least one metal selected from the group consisting of group IIA and group IIB is an oxide of at least one metal selected from magnesium, zinc and calcium, more preferably zinc oxide. The precursor of the oxide of at least one metal selected from the group IIA and IIB is a substance capable of obtaining an oxide of at least one metal selected from the group IIA and IIB under the calcination condition, for example, one or more of nitrate, acetate, carbonate, sulfate, oxalate, chloride and oxide of at least one metal selected from the group IIA and IIB. Preferably, the precursor of the oxide of at least one metal selected from groups IIA and IIB is slurried with water (deionized water) and ball-milled before or after mixing with the silica binderA step of mixing, in which ball milling is preferably performed so that the particle diameter d of the mixture is the same as that of the ball milling900.5 to 10 μm. The particle size of the raw materials is controlled to be more beneficial to the dispersion and mixing of the slurry, so that the matrix material with more uniform distribution is formed.
The preparation method according to the present invention, wherein there is no particular requirement for the selection of the silica binder precursor, may refer to the routine selection in the art as long as it has a certain viscosity and is capable of producing silica after sintering, including but not limited to silica sol, water glass, silica gel, etc., for example. Preferably, the average particle diameter of the silica binder precursor is 100nm or less. More preferably, the average particle diameter of the added silica binder precursor is 10 to 50 nm. The particle size of the raw materials is controlled to be more beneficial to the dispersion and mixing of the slurry, so that a matrix material with more uniform distribution is formed.
The preparation process according to the invention, in which the structured support used has been described in the foregoing, is described in detail with reference to the foregoing description.
According to the preparation method of the present invention, it is preferable that a step of adding a dispersant to the substrate coating slurry is further included, and the addition of the dispersant to the substrate coating slurry is advantageous for promoting the uniform stabilization of the slurry. In the invention, the dispersant is preferably an organic dispersant, and as the polymerization degree of the dispersant is generally increased, the viscosity of a solution added with the dispersant is also increased, which is beneficial to improving the firmness of the slurry after coating; along with the increase of the polymerization degree of the dispersant, the solubility of the dispersant in water is gradually reduced, which is not beneficial to the mixing of the dispersant; considering the viscosity of the slurry and the solubility of the dispersant comprehensively, the dispersant is preferably an organic dispersant with the polymerization degree of 500-2500, preferably 1000-2000; preferably, the dispersant is one or more selected from polyethylene glycol, polyglycerol, polyvinyl alcohol and polypropylene.
According to the preparation method of the present invention, the weight ratio of the dispersant to the precursor of the oxide of at least one metal selected from group IIA and IIB is preferably greater than 0 and not greater than 0.2, more preferably 0.005 to 0.02: 1; controlling the amount of the dispersant within the range is beneficial to controlling the viscosity of the slurry and prolonging the settling time of the slurry. In view of the small amount of the dispersant, it is preferable in practice to first dissolve the dispersant in water to obtain a dispersant solution and then add the dispersant solution to the substrate coating slurry. In the dispersant solution, the dispersant is preferably used in an amount of 0.5 to 30g, preferably 1 to 20g, more preferably 2 to 10g, particularly preferably 2 to 5g, based on 100mL of water.
According to the preparation method of the invention, the catalyst with a regular structure in S2 is described in the foregoing, and specific description refers to the foregoing description, and is not repeated herein. The matrix coating slurry may be distributed on the inner and/or outer surfaces of the structured support by various coating methods in the S2. The coating method may be a water coating method, a dipping method or a spraying method. The specific operation of coating can be carried out with reference to the method described in CN 1199733C. Preferably, the coating is carried out by a water coating method, namely, a method of coating the carrier by using a dispersion liquid obtained by pulping the substrate coating slurry and water, wherein one end of the carrier is immersed in the slurry liquid in the coating process, and the other end of the carrier is vacuumized so that the slurry liquid continuously passes through the pore channels of the carrier. The volume of the slurry passing through the carrier pore channel is 2-20 times of the volume of the carrier, the applied vacuum pressure is-0.1 MPa to-0.01 MPa, the coating temperature is 10-70 ℃, and the coating time is 0.1-300 seconds.
The method and conditions for drying and calcining the structured carrier coated with the matrix coating slurry in S2 according to the preparation method of the present invention are well known to those skilled in the art. For example, the drying method may be air drying, oven drying, forced air drying; the method of calcination may also be a method known in the art. Preferably, in S2, the drying temperature is between room temperature and 300 ℃, preferably between 100 and 200 ℃, and the drying time is more than 0.5h, preferably between 1 and 10 h. The roasting temperature is 400-800 ℃, and preferably 500-700 ℃; the roasting time is at least 0.5 hour, and preferably 1-10 hours.
According to the preparation method of the present invention, the transition metal precursor solution in S3 is a mixed solution formed by dissolving a transition metal precursor in a solvent, wherein the concentration of the transition metal precursor solution has no special requirement, and can be reasonably matched according to the solubility of the transition metal precursor, as long as the transition metal precursor can be completely dissolved. The solvent used therein is not particularly required in the present invention as long as it can dissolve the corresponding transition metal precursor and does not react with the prepared catalyst support. Solvents that may be used include, but are not limited to, one or more of deionized water, distilled water, and decationized water.
According to the production method of the present invention, the method of contacting the catalyst support with the transition metal precursor solution in S3 is not particularly required, and any method suitable for contacting a solid with a liquid may be employed. Such as dipping, spraying, etc. In the present invention, the catalyst support is preferably immersed in a transition metal precursor solution, and the immersion conditions are not particularly limited, and the conventional immersion may be carried out at normal temperature and normal pressure.
According to the preparation method of the present invention, preferably, the transition metal is one or more selected from Sc, Ti, V, Fe, Co, Ni, Zr, Cr, Mn, Cu, Mo and W, preferably one or more selected from Co, Ni, Mo and W. The transition metal precursor is a soluble compound capable of obtaining a transition metal oxide under a roasting condition, and preferably, the transition metal precursor is soluble salts of a transition metal such as nitrate, chloride, oxalate, acetate, ammonium salt and the like.
The method and conditions for drying and calcining the structured carrier coated with the matrix coating slurry in S3 according to the preparation method of the present invention are well known to those skilled in the art. For example, the drying method may be air drying, oven drying, forced air drying; the method of calcination may also be a method known in the art. Preferably, in step S3, the drying temperature is between room temperature and 150 ℃, preferably between 80 and 100 ℃, and the drying time is more than 1 hour, preferably between 2 and 8 hours; the roasting temperature is 200-600 ℃, preferably 200-350 ℃, and the roasting time is more than 1 hour, preferably 2-4 hours.
Preferably, the catalyst precursor obtained in step S3 includes a regular structure carrier and an active component coating precursor, and the active component coating precursor includes 5.5-76.9 wt% of transition metal oxide and 23.1-94.5 wt% of matrix, based on the total weight of the catalyst precursor; preferably, the active ingredient coating precursor comprises 11 to 58.7 wt% of a transition metal oxide and 41.3 to 89 wt% of a matrix; more preferably, the reactive component coating precursor comprises 22 to 58.7 wt% of a transition metal oxide and 41.3 to 78 wt% of a matrix; it is particularly preferred that the reactive species coating precursor comprises 33 to 58.7 wt.% transition metal oxide and 41.3 to 67 wt.% matrix.
According to the preparation method of the invention, the catalyst precursor is added in NH 43/H2And (3) carrying out reduction treatment under the atmosphere, so that the transition metal oxide formed by roasting is reduced to obtain the transition metal nitride. The reduction treatment may be carried out immediately after the preparation of the catalyst precursor, or may be carried out before the catalyst is used (i.e., before it is used for desulfurization adsorption). Preferably, the NH is3/H2The atmosphere contains 5 to 25 vol% of NH based on the total volume of the atmosphere3And 75 to 95 vol% of H2(ii) a Preferably, the catalyst contains 10 to 20 vol% of NH3And 80 to 90 vol% of H2In NH3/H2The conditions for reduction under the atmosphere include: subjecting the catalyst precursor to NH3/H2The conditions for the reduction treatment under the atmosphere include: reducing for 0.5-6 hours at the temperature of 250-550 ℃ and under the pressure of 0.2-5 MPa; preferably, the reduction treatment is carried out for 2 to 4 hours at a temperature of 300 to 450 ℃ and a pressure of 0.5 to 3.5 MPa.
According to the preparation method, comprehensive detection is carried out by a chemical element analysis method and an X-ray diffraction measurement method, wherein when the transition metal is Sc, the formed nitride is mainly ScN; when the transition metal is Ti, the formed nitride is mainly TiN; when the transition metal is V, the nitride formed is mainly VN; nitrides formed when the transition metal is FeMainly Fe3N; when the transition metal is Co, the nitride formed is mainly CoN1.2(ii) a When the transition metal is Ni, the nitride formed is mainly Ni3N; when the transition metal is Zr, the formed nitride is mainly ZrN; when the transition metal is Cr, the nitride formed is mainly Cr2N; when the transition metal is Mn, the nitride formed is mainly Mn3N2(ii) a When the transition metal is Cu, the nitride formed is mainly Cu3N; when the transition metal is Mo, the nitride formed is mainly Mo2N; when the transition metal is W, the nitride formed is mainly W2N。
Furthermore, according to the desulfurization catalyst with a regular structure of the present invention, it can be obtained by: s1, mixing and pulping the components forming the matrix with water, and drying and roasting the pulp to obtain the matrix; s2, impregnating the substrate with a solution or suspension containing a transition metal compound, introducing the transition metal compound into the substrate, drying, calcining, and reacting in NH3/H2Carrying out reduction treatment in the atmosphere to form transition metal nitride to obtain an active component; s3, grinding the obtained active component and a water-containing solvent into slurry to obtain active component coating slurry, wherein the active component coating slurry contains transition metal nitride; s4, coating the regular structure carrier with the active component slurry by a coating method, drying and roasting to obtain the desulfurization catalyst with the regular structure. The raw materials, raw material components and process methods involved in the preparation method can all refer to the related description in the preparation method of the desulfurization catalyst with the regular structure.
In addition, the invention also provides a desulfurization catalyst with a regular structure prepared by the preparation method. The catalyst comprises a regular structure carrier and an active component coating distributed on the inner surface and/or the outer surface of the regular structure carrier; the active component coating comprises 5-70 wt% of transition metal nitride and 30-95 wt% of matrix based on the total weight of the active component coating; the substrate contains 70-90 wt% of at least one metal oxide selected from IIA and IIB groups and 10-30 wt% of silicon oxide based on the total weight of the substrate. The other components of the desulfurization catalyst with the regular structure are as described above and are not described in detail herein.
Also provided in the present invention is a process for the desulfurization of sulfur-containing hydrocarbons, the process comprising: contacting a sulfur-containing hydrocarbon and a hydrogen donor with a catalyst; wherein, the catalyst is the desulfurization catalyst with the regular structure. Preferably, the structured desulfurization catalyst is present in the form of a catalyst bed.
In the desulfurization method for sulfur-containing hydrocarbon provided by the invention, the desulfurization catalyst with a regular structure can be used in a desulfurization reactor for sulfur-containing hydrocarbon as a fixed catalyst bed layer, and flowing sulfur-containing hydrocarbon and hydrogen donor can flow through the catalyst bed layer with the regular structure, namely can flow through the pore channels in the carrier with the regular structure and react with the active component coating distributed on the wall of the pore channel under the desulfurization reaction condition for sulfur-containing hydrocarbon. The sulfur-containing hydrocarbon desulfurization reactor may be a conventional reactor, and for example, may be a fixed bed reactor or the like, in which the desulfurization catalyst of the regular structure of the present invention is packed when a fixed bed reactor is used as the reactor.
In the method for desulfurizing the sulfur-containing hydrocarbon, the desulfurization catalyst with the regular structure containing the transition metal nitride is operated only under the condition of the desulfurization reaction of the sulfur-containing hydrocarbon. The desulfurization catalyst with the regular structure can be regenerated at intervals after the desulfurization effect of the sulfur-containing hydrocarbon does not meet the requirement; and the step of oxidation regeneration-reduction is not required to be repeatedly carried out, so that the metal aggregation is favorably avoided, and the desulfurization activity of the catalyst and the stability of the desulfurization process of the sulfur-containing hydrocarbon are improved.
According to the method for desulfurizing sulfur-containing hydrocarbon of the present invention, the reaction conditions for desulfurizing sulfur-containing hydrocarbon can adopt the reaction conditions for desulfurizing sulfur-containing hydrocarbon conventionally used in the field, and can also be combined with the use of a desulfurization catalyst with a regular structure, and preferably, the reaction conditions for desulfurizing sulfur-containing hydrocarbon can comprise: the reaction temperature is 200-450 ℃, the reaction pressure is 0.5-5 MPa, and the weight hourly space velocity of the sulfur-containing hydrocarbon feeding is 0.1-100 h-1The volume ratio of the hydrogen donor to the sulfur-containing hydrocarbon was 0.01 to 1000. The preferable reaction temperature is 250-400 ℃, the reaction pressure is 1-3.5 MPa, and the weight hourly space velocity of the sulfur-containing hydrocarbon feeding is 1-10 h-1The volume ratio of the hydrogen donor to the sulfur-containing hydrocarbon is 0.05 to 500. The reaction conditions can be more favorable for the desulfurization reaction of the sulfur-containing hydrocarbon, and the occurrence of adverse side reactions is reduced.
In the present invention, the sulfur-containing hydrocarbon feed weight hourly space velocity refers to the weight of sulfur-containing hydrocarbon feed per hour to the loading weight of the active component coating in the structured desulfurization catalyst.
According to the present invention, the sulfur-containing hydrocarbon may be selected from one or more of natural gas, dry gas, liquefied gas, gasoline, kerosene, diesel oil and gas oil, preferably gasoline and/or diesel oil. The above gasoline, kerosene, diesel oil and gas oil fractions are full fractions thereof and/or partially narrow fractions thereof. The sulfur content of the sulfur-containing hydrocarbon is above 50 micrograms/gram, preferably above 100 micrograms/gram. For example, the sulfur content of the sulfur-containing hydrocarbon can be 100 to 1500 micrograms/gram.
According to the present invention, the hydrogen donor is one or a mixture of two or more selected from hydrogen gas, a hydrogen-containing gas, and a hydrogen donor. The hydrogen refers to hydrogen with various purities, and the hydrogen-containing gas is preferably one or more of catalytic cracking (FCC) dry gas, coking dry gas and thermal cracking dry gas. The volume content of hydrogen in the hydrogen-containing gas is more than 30 volume percent, and the hydrogen donor is selected from at least one of tetrahydronaphthalene, decahydronaphthalene and indane.
In the present invention, the pressures involved are all expressed as gauge pressures.
The desulfurization catalyst with a regular structure and the preparation method thereof and the desulfurization method of sulfur-containing hydrocarbon according to the present invention will be described in detail by way of examples.
The sulfur content was measured in the following examples and comparative examples by off-line chromatographic analysis using a GC6890-SCD instrument from the company agilent. Motor Octane Number (MON) and Research Octane Number (RON) of the reaction raw material catalytically cracked gasoline and the product gasoline after the desulfurization catalyst is stabilized were measured by GB/T503-1995 and GB/T5487-1995.
In the following examples and comparative examples, the method for coating the substrate slurry on the regular structure carrier is a water coating method, and the specific process method comprises the following steps: in each coating process, one end of the regular structure carrier is immersed in the matrix coating slurry, and the other end of the regular structure carrier is vacuumized to enable the slurry to continuously pass through the pore channel of the carrier; wherein the volume of the slurry passing through the carrier pore channel is 2.5 times of the volume of the carrier, the applied vacuum pressure is-0.03 MPa (MPa), the coating temperature is 35 ℃, and the coating time is 60-120 seconds.
Example 1
This example serves to illustrate the desulfurization catalyst of regular structure and the preparation method thereof according to the present invention.
(1) Preparation of matrix coating slurry:
1.01kg of zinc oxide powder (product of Beijing chemical plant, containing 1kg of dry basis) and 1kg of deionized water are mixed uniformly, and the mixture is ball-milled by a wet method to obtain grinding slurry (particle diameter d)908 μm); adding 1.67kg of water glass (produced by Zhongpetrochemical catalyst Qilu division, modulus is 3.2, average particle diameter is 30nm, and silicon oxide is 0.25kg) into the grinding slurry, stirring for 10min, adding 500mL of polyethylene glycol solution (prepared by adding 2g of polyethylene glycol into 100mL of water, wherein the polyethylene glycol is produced by Allantin reagent company, polymerization degree is 1700, and analytically pure, the same below), and stirring for 20min to obtain a matrix coating slurry with solid content of 30 wt%;
(2) preparation of catalyst carrier:
the substrate coating slurry prepared as described above was applied to 1.18kg of a cylindrical honeycomb cordierite carrier (available from Jiangsu Yixing non-metallic chemical mechanical works Co., Ltd., size: 1.18 kg)
The open porosity was 70%, the cell density of the cross section was 200 cells/square inch, and the cross sectional area of the cells was 5625 μm2The same applies below), blowing off the outer surface of the honeycomb carrier by compressed air (the pressure is 0.4MPa, the same applies below), drying the coated carrier at 120 ℃ for 120min, and roasting at 650 ℃ for 60 min; the above coating, drying and calcining processes were repeated to obtain 1.52kg of a catalyst support.
(3) Preparation of the catalyst precursor:
1.01kg of ammonium paramolybdate tetrahydrate (NH)4)6Mo7O24·4H2O (molecular weight 1235.86, analytical grade) was dissolved in 2L of deionized water to obtain an aqueous solution of ammonium molybdate. The prepared catalyst carrier is immersed in an ammonium molybdate aqueous solution for 5min, taken out and dried at 100 ℃ for 120min, calcined at 300 ℃ for 120min, and the immersion, drying and calcination procedures are repeated to obtain 1.76kg of 1.52kg of catalyst precursor.
(4) Reduction treatment:
the catalyst precursor was added at 10 vol% NH390% by volume of H2And reducing for 4h at the temperature of 300 ℃ and under the pressure of 2MPa in the atmosphere to obtain 1.69kg of desulfurization catalyst A1 with a regular structure.
(5) Composition of desulfurization catalyst a1 with regular structure:
the desulfurization catalyst A1 having a regular structure contained, by dry weight, 70% by weight of cordierite, 16% by weight of zinc oxide, 4% by weight of silicon oxide, and 10% by weight of molybdenum nitride.
Example 2
This example serves to illustrate the desulfurization catalyst of regular structure and the preparation method thereof according to the present invention.
(1) Preparation of matrix coating slurry:
1.53kg of zinc oxide powder (product of Beijing chemical plant, containing 1.5kg of dry basis) and 1kg of deionized water were uniformly mixed, and wet ball-milled to obtain a milling slurry (particle diameter d)908 μm); adding 0.68kg of silica sol (0.17 kg of silicon dioxide produced by Zhongpetrochemical catalyst Qilu division) into the grinding slurry, stirring for 10min, wet-grinding for 5h by using a ball mill, adding 375mL of polyethylene glycol solution (prepared by adding 2g of polyethylene glycol into 100mL of water to dissolve the polyethylene glycol, wherein the polyethylene glycol is produced by an Aradin reagent company, the polymerization degree is 1700, the analytically pure product is the same as the following), and stirring for 20min to obtain matrix coating slurry with the solid content of 30 wt%;
(2) preparation of catalyst carrier:
coating the prepared substrate coating slurry on a 1.18kg cylindrical honeycomb cordierite carrier, drying the coated carrier at 100 ℃ for 150min, and then roasting at 500 ℃ for 240 min; the above coating, drying and calcining processes were repeated to obtain 1.33kg of a catalyst support.
(3) Preparation of the catalyst precursor:
mixing a cobalt nitrate solution, 3.65kg of nickel nitrate hexahydrate (the molar ratio of Co to Ni is 1: 5) and 2L of deionized water to form a Co-Ni aqueous solution, soaking the prepared catalyst support in the Co-Ni aqueous solution for 2min, taking out the catalyst support, drying the catalyst support at 80 ℃ for 120min, roasting the catalyst support at 350 ℃ for 60min, and repeating the soaking, drying and roasting procedures to obtain 1.50kg of a catalyst precursor;
(4) reduction treatment:
the catalyst precursor was added at 20 vol% NH380% by volume H2And reducing for 2h at 425 ℃ and 1MPa in the atmosphere to obtain 1.48kg of desulfurization catalyst A2 with a regular structure.
(5) Composition of desulfurization catalyst a2 with regular structure:
the desulfurization catalyst A2 having a regular structure contained cordierite at 80 wt%, zinc oxide at 9 wt%, silica at 1 wt%, cobalt nitride at 1.7 wt%, and nickel nitride at 8.3 wt% based on the dry weight of the catalyst.
Example 3
This example serves to illustrate the desulfurization catalyst of regular structure and the preparation method thereof according to the present invention.
(1) Preparation of matrix coating slurry:
1.01kg of zinc oxide powder (product of Beijing chemical plant, containing 1kg of dry basis) and 1kg of deionized water were uniformly mixed, and wet ball-milled to obtain a milling slurry (particle diameter d)908 μm); adding 2.89kg of water glass (produced by Zhongpetrochemical catalyst Qilu division, modulus is 3.2, average particle diameter is 30nm, and silicon oxide is 0.43kg) into the grinding slurry, stirring for 10min, adding 1000mL of polyethylene glycol solution (prepared by adding 2g of polyethylene glycol into 100mL of water, wherein the polyethylene glycol is produced by Allantin reagent company, polymerization degree is 1700, and analytically pure, the same below), and stirring for 20min to obtain a matrix coating slurry with solid content of 30 wt%;
(2) preparation of catalyst carrier:
coating the prepared matrix coating slurry on a 1.18kg cylindrical honeycomb cordierite carrier, blowing the outer surface of the coated catalyst with compressed air (pressure of 0.4MPa, the same below) to clean the honeycomb carrier, drying the coated carrier at 120 ℃ for 120min, and calcining at 650 ℃ for 60 min; the above coating, drying and calcining processes were repeated to obtain 1.32kg of a catalyst support.
(3) Preparation of the catalyst precursor:
393.12g of ammonium paratungstate (product of national chemical group, Beijing Co., Ltd., molecular weight 1419.57, analytical purity) was dissolved in 2L of deionized water to obtain an aqueous solution of ammonium paratungstate. The prepared catalyst carrier is immersed in an ammonium paratungstate aqueous solution for 5min, taken out, dried at 100 ℃ for 120min, roasted at 300 ℃ for 120min, and the immersion, drying and roasting processes are repeated to obtain 1.4kg of catalyst precursor.
(4) Reduction treatment:
the catalyst precursor was added at 20 vol% NH380% by volume H2The reaction mixture was reduced at 425 ℃ and 1MPa for 3 hours under an atmosphere to obtain 1.39kg of desulfurization catalyst A3 with a regular structure.
(5) Composition of desulfurization catalyst a3 with regular structure:
the desulfurization catalyst A3 having a regular structure contained 85 wt% of cordierite, 7 wt% of zinc oxide, 3 wt% of silica and 5 wt% of tungsten nitride based on the dry weight of the catalyst.
Example 4
This example serves to illustrate the desulfurization catalyst of regular structure and the preparation method thereof according to the present invention.
(1) Preparation of matrix coating slurry: referring to example 1, except that 1.02kg of magnesium oxide (from Beijing chemical plant, average particle diameter of 500 nm; containing 1kg of dry basis) was used in place of the zinc oxide powder;
(2) preparation of catalyst carrier: referring to example 1, except that the matrix coating slurry prepared in the foregoing step (1) was used in place of the matrix coating slurry prepared in the step (1) of example 1, 1.52kg of a catalyst support was obtained;
(3) preparation of the catalyst precursor: referring to example 1, except for using the catalyst support obtained in the foregoing step (2) instead of the catalyst support prepared in the step (2) of example 1, 1.76kg of 1.52kg of a catalyst precursor was obtained;
(4) reduction treatment: referring to example 1, except for using the catalyst precursor obtained in the foregoing step (3) in place of the catalyst precursor prepared in the step (3) of example 1, 1.69kg of desulfurization catalyst A4 of a regular structure was obtained.
(5) Composition of desulfurization catalyst a4 with regular structure:
the desulfurization catalyst A4 having a regular structure contained cordierite in an amount of 70 wt%, magnesia in an amount of 16 wt%, silica in an amount of 4 wt%, and molybdenum nitride in an amount of 10 wt% based on the dry weight of the catalyst.
Example 5
This example serves to illustrate the desulfurization catalyst of regular structure and the preparation method thereof according to the present invention.
(1) Preparation of matrix coating slurry: referring to example 1, except that 1.02kg of calcium oxide (available from Beijing chemical plant, average particle diameter of 200 nm; containing 1kg of dry basis) was used in place of the zinc oxide powder;
(2) preparation of catalyst carrier: referring to example 1, except that the matrix coating slurry prepared in the foregoing step (1) was used in place of the matrix coating slurry prepared in the step (1) of example 1, 1.52kg of a catalyst support was obtained;
(3) preparation of the catalyst precursor: referring to example 1, except for using the catalyst support obtained in the foregoing step (2) instead of the catalyst support prepared in the step (2) of example 1, 1.76kg of 1.52kg of a catalyst precursor was obtained;
(4) reduction treatment: referring to example 1, except for using the catalyst precursor obtained in the foregoing step (3) in place of the catalyst precursor prepared in the step (3) of example 1, 1.69kg of desulfurization catalyst A5 of a regular structure was obtained.
(5) Composition of desulfurization catalyst a5 with regular structure:
the desulfurization catalyst A5 having a regular structure contained cordierite in an amount of 70 wt%, calcium oxide in an amount of 16 wt%, silica in an amount of 4 wt%, and molybdenum nitride in an amount of 10 wt% based on the dry weight of the catalyst.
Example 6
This example serves to illustrate the desulfurization catalyst of regular structure and the preparation method thereof according to the present invention.
(1) Preparation of matrix coating slurry: the same as example 1;
(2) preparation of catalyst carrier: the same as example 1;
(3) preparation of the catalyst precursor: referring to example 1, except that 1.08kg of ammonium metavanadate (manufactured by national institute of medicine, molecular weight 116.98, analytical grade) was dissolved in 2L of deionized water to obtain an aqueous solution of ammonium metavanadate. Soaking the prepared catalyst carrier in ammonium metavanadate aqueous solution for 5min, taking out, drying at 95 ℃ for 120min, roasting at 320 ℃ for 120min, and repeating the soaking, drying and roasting procedures to obtain 1.76kg of catalyst precursor.
(4) Reduction treatment:
the catalyst precursor was added at 20 vol% NH380% by volume H2The reaction mixture was reduced at 425 ℃ and 1MPa for 3 hours under an atmosphere to obtain 1.69kg of desulfurization catalyst A6 with a regular structure.
(5) Composition of desulfurization catalyst a6 with regular structure:
the desulfurization catalyst A6 having a regular structure contained cordierite in an amount of 70 wt%, zinc oxide in an amount of 16 wt%, silica in an amount of 4 wt%, and vanadium nitride in an amount of 10 wt% based on the dry weight of the catalyst.
Example 7
This example serves to illustrate the desulfurization catalyst of regular structure and the preparation method thereof according to the present invention.
(1) Preparation of matrix coating slurry: referring to example 1, except that a matrix coating slurry was prepared by adding 1000mL of polyethylene glycol solution (prepared by adding 20g of polyethylene glycol per 100mL of water dissolved) in an amount of 0.2: 1;
(2) preparation of catalyst carrier: referring to example 1, except that the matrix coating slurry prepared in the foregoing step (1) was used in place of the matrix coating slurry prepared in the step (1) of example 1, 1.52kg of a catalyst support was obtained;
(3) preparation of the catalyst precursor: referring to example 1, except for using the catalyst support prepared in the foregoing step (2) instead of the catalyst support prepared in the step (2) of example 1, 1.76kg of the catalyst precursor was obtained;
(4) reduction treatment: referring to example 1, except for using the catalyst precursor prepared in the foregoing step (3) in place of the catalyst precursor prepared in the step (3) of example 1, 1.69kg of desulfurization catalyst A7 of a regular structure was obtained.
(5) Composition of desulfurization catalyst a7 with regular structure:
the desulfurization catalyst A7 having a regular structure contained cordierite in an amount of 70 wt%, zinc oxide in an amount of 16 wt%, silica in an amount of 4 wt%, and molybdenum nitride in an amount of 10 wt% based on the dry weight of the catalyst.
Example 8
This example serves to illustrate the desulfurization catalyst of regular structure and the preparation method thereof according to the present invention.
(1) Preparation of matrix coating slurry: referring to example 1, except that no polyethylene glycol solution was added during the preparation of the matrix coating slurry;
(2) preparation of catalyst carrier: referring to example 1, except that the matrix coating slurry prepared in the foregoing step (1) was used in place of the matrix coating slurry prepared in the step (1) of example 1, 1.52kg of a catalyst support was obtained;
(3) preparation of the catalyst precursor: referring to example 1, except for using the catalyst support prepared in the foregoing step (2) instead of the catalyst support prepared in the step (2) of example 1, 1.76kg of the catalyst precursor was obtained;
(4) reduction treatment: referring to example 1, except for using the catalyst precursor prepared in the foregoing step (3) in place of the catalyst precursor prepared in the step (3) of example 1, 1.69kg of desulfurization catalyst A8 of a regular structure was obtained.
(5) Composition of desulfurization catalyst A8 with regular structure:
the desulfurization catalyst A8 having a regular structure contained cordierite in an amount of 70 wt%, zinc oxide in an amount of 16 wt%, silica in an amount of 4 wt%, and molybdenum nitride in an amount of 10 wt% based on the dry weight of the catalyst.
Example 9
This example serves to illustrate the desulfurization catalyst of regular structure and the preparation method thereof according to the present invention.
(1) Preparation of the matrix material:
1.01kg of zinc oxide powder (product of Beijing chemical plant, containing 1.0kg of dry basis) and 1kg of deionized water were mixed uniformly and ball-milled by a wet method to obtain a milling slurry (particle diameter d)908 μm); adding 1.67kg of water glass (produced by Zhongpetrochemical catalyst Qilu division, modulus is 3.2, average particle diameter is 3nm, and silicon oxide is 0.25kg) into the grinding slurry, stirring for 10min, adding 500mL of polyethylene glycol solution (prepared by adding 2g of polyethylene glycol into 100mL of water), stirring for 20min to obtain matrix coating slurry with solid content of 30 wt%, drying the matrix coating slurry at 120 ℃ for 120min, and roasting at 550 ℃ for 180min to obtain a matrix material;
(2) preparation of active ingredients:
1.01kg of ammonium paramolybdate tetrahydrate (NH)4)6Mo7O24·4H2O (molecular weight 1235.86, analytical grade) was dissolved in 2L of deionized water to obtain an aqueous solution of ammonium molybdate. Soaking the 1.01kg of matrix material in ammonium molybdate aqueous solution for 5min, taking out, drying at 100 deg.C for 120min, roasting at 300 deg.C for 120min, and repeating the soaking, drying and roasting procedures to obtain 1.72kg of the active component;
(3) preparation of the catalyst precursor:
wet-milling the active components by a ball mill for 5h to prepare slurry with the solid content of 30%, coating the slurry on a 1.18kg cylindrical honeycomb cordierite carrier, drying the carrier at 120 ℃ for 120min, roasting the carrier at 550 ℃ for 180min, and repeating the steps of dipping, drying and roasting to obtain 1.76kg of catalyst precursor;
(4) reduction treatment:
the catalyst precursor was added at 10 vol% NH390% by volume of H2And reducing for 4h at the temperature of 300 ℃ and under the pressure of 2MPa in the atmosphere to obtain 1.69kg of desulfurization catalyst A9 with a regular structure.
(6) Composition of desulfurization catalyst a9 with regular structure:
the desulfurization catalyst A9 having a regular structure contained cordierite in an amount of 70 wt%, zinc oxide in an amount of 16 wt%, silica in an amount of 4 wt%, and molybdenum nitride in an amount of 10 wt% based on the dry weight of the catalyst.
Comparative example 1
This comparative example is used for comparative illustration of the desulfurization catalyst of regular structure of the present invention and the preparation method thereof.
(1) Preparation of matrix coating slurry: the same as example 1;
(2) preparation of catalyst carrier: the same as example 1;
(3) preparation of the catalyst precursor:
1.01kg of ammonium paramolybdate tetrahydrate (NH)4)6Mo7O24·4H2O (molecular weight 1235.86, analytical grade) was dissolved in 2L of deionized water to obtain an aqueous solution of ammonium molybdate. Soaking the prepared catalyst carrier in ammonium molybdate aqueous solution for 5min, taking out, drying at 100 deg.C for 120min, calcining at 300 deg.C for 120min, and repeating the soaking, drying and calcining steps to obtain 1.78kg of catalyst precursor;
(4) reduction treatment:
the foregoing catalyst precursor was reduced with a gas containing 96 vol% hydrogen at a temperature of 300 ℃ and a pressure of 2MPa for 4 hours to obtain 1.69kg of desulfurization catalyst B of a regular structure.
(5) Composition of desulfurization catalyst B with a regular structure:
the desulfurization catalyst B of a regular structure contained, based on its dry weight, 70% by weight of cordierite, 16% by weight of zinc oxide, 4% by weight of silicon oxide and 10% by weight of metallic molybdenum.
Application example
Desulfurization evaluation experiments were performed on the desulfurization catalysts a1-a9 and B of the regular structures prepared according to examples 1 to 9 and comparative example 1 of the present invention using a fixed bed micro-reaction experimental apparatus, specifically including: 16g of a desulfurization catalyst was packed in a fixed bed reactor having an inner diameter of 30 mm. Hydrogen is used as hydrogen supply medium, the reaction temperature is 400 ℃, the reaction pressure is 1.38MPa, the hydrogen flow is 6.3L/h, the gasoline flow is 80mL/h, and the raw material hydrocarbon oilThe weight space velocity of (A) is 4h-1The desulfurization reaction of sulfur-containing hydrocarbon oil (gasoline) was carried out under the desulfurization reaction conditions of sulfur-containing hydrocarbon, and the composition of the gasoline is shown in table 1.
Evaluation of desulfurization Performance:
(1) measuring the composition of the product gasoline by adopting a gas chromatography POINA method, and recording corresponding data in tables 2 and 3;
(2) calculating the yield of the product gasoline by a weighing method, and recording corresponding data in tables 2 and 3;
(3) motor Octane Number (MON) and Research Octane Number (RON) of the pre-reaction and post-reaction mixed gasoline were measured using GB/T503-;
(4) the sulfur content in the product gasoline was measured using the total sulfur assay (coulometry) in the petrochemical industry standard SH/T0253-1992 light petroleum products, and the change in sulfur content in the product gasoline with reaction time was recorded in tables 2 and 3.
TABLE 1
| Item | Analyzing data | Item | Analyzing data |
| Density (20 ℃ C.) (kg.m)-3) | 727.3 | Induction phase (min) | 922 |
| Actual gum (mg/mL) | 0.34 | Distillation range (. degree.C.) | |
| Refractive index (20 ℃ C.) | 1.4143 | Initial boiling point | 38.5 |
| Sulfur content (ng./. mu.L) | 960.48 | 5％ | 49.0 |
| Mercaptan sulfur content (ng/. mu.L) | 10.2 | 10％ | 55.5 |
| Hydrogen sulfide content (ng/. mu.L) | 0 | 30％ | 74.7 |
| Octane number (RON/MON) | 93.7/83.6 | 50％ | 97.2 |
| Group composition volume (%) | 70％ | 124.2 | |
| Saturated hydrocarbons | 44.0 | 90％ | 155.2 |
| Olefins | 41.2 | 95％ | 165.2 |
| Aromatic hydrocarbons | 14.8 | End point of distillation | 185.0 |
| Isomeric hydrocarbons | 35.1 | ||
| Benzene and its derivatives | 1.16 |
Table 2.
Table 3.
Note:
1. the feed gasoline had a sulfur content of 960ppm, a RON of 93.7 and a MON of 83.6.
2.Δ MON represents the increase in product gasoline MON compared to the gasoline feedstock;
3.Δ RON represents the increase in the RON of the product gasoline compared to the gasoline feedstock;
4. and delta (RON + MON)/2 represents the difference between the antiknock index of the product gasoline and the antiknock index of the raw gasoline.
As can be seen from the result data in tables 2 and 3, after the gasoline desulfurization treatment is performed by using the catalyst B prepared in comparative example 1, the sulfur content in the gasoline product is lower than 0.5ppm (chromatographic detection limit) in the initial stage of the reaction, and gradually increases with the progress of the reaction time, but after the reaction for 24h to 96h, the sulfur content in the gasoline product reaches 14.8ppm, which exceeds the marginal requirement (10ppm) of the sulfur content in the gasoline product, and the catalyst needs to be regenerated. Moreover, the gasoline product produced in the process had a saturated hydrocarbon content of 62 wt%, an iso-hydrocarbon content of 35 wt%, a benzene content of 0.76 wt%, and an octane number loss of 0.52 units.
After the desulfurization catalyst A1-A9 with the regular structure prepared in the examples 1-9 is used as a catalyst for gasoline desulfurization treatment, the sulfur content in a gasoline product is lower than 0.5ppm (chromatographic detection limit) in the initial reaction stage, the sulfur content in the product gradually increases along with the reaction time, but the sulfur content in the gasoline product is only 6.5ppm at most after 24-96 h of reaction; at the same time, the resulting gasoline product had saturated hydrocarbons in the range of 47 wt.% to 58 wt.% (reduced relative to comparative example 1), iso-hydrocarbon content in the range of 37 wt.% to 45 wt.% (increased relative to comparative example 1), benzene content in the range of 0.39 wt.% to 0.59 wt.% (reduced relative to comparative example 1); and the octane number loss of the obtained gasoline product is only 0.1 unit on average (reduced relative to the comparative example 1).
In conclusion, the desulfurization catalyst with the regular structure provided by the invention has better desulfurization activity and activity stability. Moreover, compared with the prior desulfurization technology, the desulfurization catalyst with the regular structure provided by the invention can reduce the content of saturated hydrocarbon and benzene in the desulfurized oil product, improve the content of isomeric hydrocarbon and improve the octane number of the desulfurized oil product (namely the octane number loss is obviously reduced).
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various features described in the above embodiments may be combined in any suitable manner without departing from the scope of the invention. The invention is not described in detail in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (38)
1. A desulfurization catalyst with a regular structure comprises a regular structure carrier and an active component coating distributed on the inner surface and/or the outer surface of the regular structure carrier; the active component coating comprises 5-70 wt% of transition metal nitride and 30-95 wt% of matrix based on the total weight of the active component coating; the substrate contains 70-90 wt% of at least one metal oxide selected from IIA and IIB and 10-30 wt% of silicon oxide based on the total weight of the substrate;
wherein the transition metal is one or more selected from Sc, Ti, V, Fe, Co, Ni, Zr, Cr, Mn, Cu, Mo and W.
2. The catalyst according to claim 1, wherein the active component coating layer is contained in an amount of 10 to 50 wt% based on the total weight of the structured desulfurization catalyst.
3. The catalyst according to claim 2, wherein the active component coating layer is contained in an amount of 15 to 30 wt% based on the total weight of the structured desulfurization catalyst.
4. The catalyst according to any one of claims 1 to 3, wherein the active component coating layer comprises 10 to 50 wt% of the transition metal nitride and 50 to 90 wt% of the matrix, based on the total weight of the active component coating layer.
5. The catalyst according to claim 4, wherein the active component coating layer comprises 20 to 50 wt% of the transition metal nitride and 50 to 80 wt% of the matrix, based on the total weight of the active component coating layer.
6. The catalyst according to claim 5, wherein the active component coating layer comprises 30 to 50 wt% of the transition metal nitride and 50 to 70 wt% of the matrix, based on the total weight of the active component coating layer.
7. The catalyst according to any one of claims 1 to 3,
the oxide of at least one metal selected from IIA and IIB is an oxide of at least one metal selected from magnesium, zinc and calcium;
the regular structure carrier is selected from a monolithic carrier with a parallel pore channel structure with two open ends.
8. The catalyst according to any one of claims 1 to 3, wherein the cross-section of the structured carrier has a pore density of 40 to 800 pores per square inch, and the cross-sectional area of each pore in the structured carrier is 400 to 1.8 × 105μm2。
9. The catalyst of any one of claims 1-3, wherein the structured carrier is selected from at least one of a cordierite honeycomb carrier, a mullite honeycomb carrier, a diamond honeycomb carrier, a corundum honeycomb carrier, a zirconia corundum honeycomb carrier, a quartz honeycomb carrier, a nepheline honeycomb carrier, a feldspar honeycomb carrier, an alumina honeycomb carrier, and a metal alloy honeycomb carrier.
10. A preparation method of a desulfurization catalyst with a regular structure is characterized by comprising the following steps:
s1, mixing a precursor of an oxide of at least one metal selected from IIA and IIB groups with a silicon oxide binder precursor to prepare a matrix coating slurry;
s2, coating the slurry of the matrix coating on a regular structure carrier, drying and roasting to form a matrix coating on the inner surface and/or the outer surface of the regular structure carrier to obtain a catalyst carrier;
s3, contacting the catalyst supporter with a transition metal precursor solution, drying and roasting after the contact to form a transition metal oxide on the matrix coating to obtain a catalyst precursor;
s4, adding the catalyst precursor into NH3/H2Carrying out reduction treatment under the atmosphere to reduce the transition metal oxide to form transition metal nitride, so as to obtain the desulfurization catalyst with the regular structure;
the transition metal in the transition metal precursor solution is one or more selected from Sc, Ti, V, Fe, Co, Ni, Zr, Cr, Mn, Cu, Mo and W, and the transition metal precursor is nitrate, chloride, oxalate, acetate or ammonium salt of the transition metal;
wherein the total content of the matrix coating and the transition metal nitride is 10-50 wt% based on the total weight of the desulfurization catalyst with the regular structure;
the content of the transition metal nitride is 5-70 wt% and the content of the matrix coating is 30-95 wt% based on the total content of the matrix coating and the transition metal nitride;
the base coating slurry contains 70 to 90 wt% of a precursor of an oxide of at least one metal selected from groups IIA and IIB, calculated as metal oxide, and 10 to 30 wt% of a silica binder precursor, calculated as silica, calculated as dry weight thereof.
11. The method of claim 10 wherein the matrix coating layer and the transition metal nitride are present in a total amount of 15 to 30 wt.%, based on the total weight of the structured desulfurization catalyst.
12. The method according to claim 10, wherein the transition metal nitride is contained in an amount of 10 to 50 wt% and the matrix coating layer is contained in an amount of 50 to 90 wt%, based on the total content of the matrix coating layer and the transition metal nitride.
13. The method according to claim 10, wherein the transition metal nitride is contained in an amount of 20 to 50 wt% and the matrix coating is contained in an amount of 50 to 80 wt%, based on the total content of the matrix coating and the transition metal nitride.
14. The method according to claim 10, wherein the transition metal nitride is contained in an amount of 30 to 50 wt% and the matrix coating is contained in an amount of 50 to 70 wt%, based on the total content of the matrix coating and the transition metal nitride.
15. The method of any of claims 10-14, wherein the S1 further comprises the step of adding a dispersant to the matrix coating slurry.
16. The method according to claim 15, wherein the dispersant is an organic dispersant having a degree of polymerization in the range of 500 to 2500.
17. The method according to claim 15, wherein the dispersant is an organic dispersant having a degree of polymerization in the range of 1000 to 2000.
18. The method of claim 15, wherein the dispersant is one or more of polyethylene glycol, polyglycerol, polyvinyl alcohol and polypropylene.
19. The method as claimed in claim 15, wherein the weight ratio of the dispersant to the precursor of the oxide of at least one metal selected from groups IIA and IIB is greater than 0 and equal to or less than 0.2.
20. The method as claimed in claim 15, wherein the weight ratio of the dispersant to the precursor of the oxide of at least one metal selected from groups IIA and IIB is 0.005 to 0.02: 1.
21. the method of any one of claims 10-14,
the drying temperature in the S2 is between room temperature and 300 ℃, and the drying time is more than 0.5 h; the roasting temperature is 400-800 ℃, and the roasting time is more than 0.5 h;
the drying temperature in the S3 is between room temperature and 150 ℃, and the drying time is more than 1 h; the roasting temperature is 200-600 ℃, and the roasting time is more than 1 h.
22. The method according to claim 21, wherein the temperature for drying in S2 is 100-200 ℃.
23. The method according to claim 21, wherein the drying time in S2 is 1-10 h.
24. The method as claimed in claim 21, wherein the temperature of the calcination in S2 is 500-700 ℃.
25. The method as claimed in claim 21, wherein the roasting time in S2 is 1-10 h.
26. The method according to claim 21, wherein the temperature of the drying in S3 is 80-100 ℃.
27. The method according to claim 21, wherein the drying time in S3 is 2-8 h.
28. The method as claimed in claim 21, wherein the temperature of the calcination in S3 is 200-350 ℃.
29. The method as claimed in claim 21, wherein the roasting time in S3 is 2-4 h.
30. The method according to any one of claims 10 to 14, wherein the conditions of the reduction treatment in S4 include: reducing for 0.5-6 hours at 250-550 ℃ and 0.2-5 MPa.
31. The method as claimed in claim 30, wherein the conditions of the reduction treatment in S4 include: reducing for 2-4 hours at the temperature of 300-450 ℃ and under the pressure of 0.5-3.5 MPa.
32. The method of any one of claims 10-14, wherein NH at S43/H2The atmosphere contains 5 to 25 vol% of NH based on the total volume of the atmosphere3And 75 to 95 vol% of H2。
33. The method of claim 32, wherein NH at S43/H2The atmosphere contains 10 to 20 vol% of NH based on the total volume of the atmosphere3And 80 to 90 vol% of H2。
34. The method of any one of claims 10-14,
the oxide of at least one metal selected from IIA and IIB is an oxide of at least one metal selected from magnesium, zinc and calcium;
the silicon oxide binder precursor is one or more of silica sol, water glass or silica gel;
the regular structure carrier is selected from a monolithic carrier with a parallel pore channel structure with two open ends.
35. The process as set forth in any one of claims 10 to 14 wherein the structured carrier has a cross-sectional area having a pore density of from 40 to 800 pores per square inch and a cross-sectional area of from 400 to 1.8 × 105μm2。
36. The method of any of claims 10-14, wherein the structured carrier is selected from at least one of a cordierite honeycomb carrier, a mullite honeycomb carrier, a diamond honeycomb carrier, a corundum honeycomb carrier, a zirconia corundum honeycomb carrier, a quartz honeycomb carrier, a nepheline honeycomb carrier, a feldspar honeycomb carrier, an alumina honeycomb carrier, and a metal alloy honeycomb carrier.
37. A desulfurization catalyst with a structured structure prepared by the method of any one of claims 10 to 36.
38. A process for the desulfurization of sulfur-containing hydrocarbons, the process comprising: contacting a sulfur-containing hydrocarbon and a hydrogen donor with a catalyst; wherein the catalyst is the desulfurization catalyst with a regular structure as set forth in any one of claims 1 to 9 and 37.
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| CN101099934A (en) * | 2006-07-04 | 2008-01-09 | 中国石油天然气股份有限公司 | Aromatic saturated hydrogenation catalyst and its preparing process |
| CN104549303A (en) * | 2013-10-29 | 2015-04-29 | 中国石油化工股份有限公司 | Catalyst system for sulfur-hydrocarbon-containing desulfurization, sulfur-hydrocarbon-containing desulfurization method and device for method |
| CN105214704A (en) * | 2015-10-29 | 2016-01-06 | 无锡桥阳机械制造有限公司 | A kind of preparation method of catalyst |
| CN106140176B (en) * | 2015-04-28 | 2018-09-28 | 中国石油化工股份有限公司 | The method of the catalyst system and sulfur-bearing hydrocarbon desulfurization of sulfur-bearing hydrocarbon desulfurization |
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