CN114425448B - Hydrodesulfurization catalyst and preparation method and application thereof - Google Patents

Hydrodesulfurization catalyst and preparation method and application thereof Download PDF

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CN114425448B
CN114425448B CN202011106764.0A CN202011106764A CN114425448B CN 114425448 B CN114425448 B CN 114425448B CN 202011106764 A CN202011106764 A CN 202011106764A CN 114425448 B CN114425448 B CN 114425448B
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catalyst
molybdenum
reaction
hydrodesulfurization
temperature
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CN114425448A (en
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蒋淑娇
袁胜华
杨刚
张�成
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Sinopec Dalian Petrochemical Research Institute Co ltd
China Petroleum and Chemical Corp
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China Petroleum and Chemical Corp
Sinopec Dalian Research Institute of Petroleum and Petrochemicals
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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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/20—Carbonyls
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
    • B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
    • B01J31/1825—Ligands comprising condensed ring systems, e.g. acridine, carbazole
    • B01J31/183—Ligands comprising condensed ring systems, e.g. acridine, carbazole with more than one complexing nitrogen atom, e.g. phenanthroline
    • 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
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/613—10-100 m2/g
    • 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
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/615—100-500 m2/g
    • 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
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/633—Pore volume less than 0.5 ml/g
    • 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
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/635—0.5-1.0 ml/g
    • 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
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/638—Pore volume more than 1.0 ml/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/20—Sulfiding
    • 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
    • C10G45/06—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 containing nickel or cobalt metal, or compounds thereof
    • C10G45/08—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 containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
    • 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
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
    • B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
    • B01J2531/0241—Rigid ligands, e.g. extended sp2-carbon frameworks or geminal di- or trisubstitution
    • B01J2531/025—Ligands with a porphyrin ring system or analogues thereof, e.g. phthalocyanines, corroles
    • 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
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/84—Metals of the iron group
    • B01J2531/845—Cobalt
    • 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
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/84—Metals of the iron group
    • B01J2531/847—Nickel
    • 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
    • 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
    • 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
    • C10G2300/70—Catalyst aspects
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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  • General Chemical & Material Sciences (AREA)
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Abstract

The invention discloses a hydrodesulfurization catalyst and a preparation method and application thereof. The catalyst comprises: the catalyst comprises a carrier, molybdenum element and VIII group metal element, wherein the molybdenum element exists in the catalyst at least partially in the form of carbonyl molybdenum, and the VIII group metal element exists in the catalyst in the form of VIII group metalloporphyrin compound. The hydrodesulfurization catalyst is used in the hydrodesulfurization process of a heavy oil fixed bed, can be used for selectively hydrogenating and removing sulfur-containing compounds, can reduce the consumption of hydrogen and save energy, and can be used in the process of producing marine fuel oil by hydrogenating the heavy oil fixed bed.

Description

Hydrodesulfurization catalyst and preparation method and application thereof
Technical Field
The invention belongs to the field of petrochemical industry, relates to a hydrodesulfurization catalyst and a preparation method thereof, in particular to a heavy oil selective hydrodesulfurization catalyst and a preparation method thereof, and is particularly suitable for producing low-sulfur marine fuel oil or low-sulfur marine fuel oil blending components by taking secondary processed heavy oil as a raw material.
Background
With the rise of environmental protection requirements, the sulfur content limitation requirements of marine fuel oil are more strict. One of the effective means of reducing the sulfur content of fuel oils is hydrotreating. For heavy oil processed secondarily, the raw material contains a large amount of unsaturated hydrocarbon, and excessive hydrogenation saturation of the unsaturated hydrocarbon consumes a large amount of hydrogen to cause unnecessary waste, and selective removal of sulfides in the heavy oil can reduce the consumption of hydrogen and save energy.
At present, the heavy oil hydrodesulfurization catalyst mainly adopts a residual oil hydrodesulfurization catalyst, but the conventional residual oil hydrodesulfurization catalyst does not have good selectivity, so that deep desulfurization is achieved, and meanwhile, aromatic hydrocarbon and the like are often excessively saturated, so that the processing cost is increased, and the property of ship combustion is influenced.
CN1903994a discloses a method for producing fuel oil by hydro-upgrading coal tar as a raw material. In the method, the main hydrogenation catalyst adopts porous refractory oxide as a carrier, the content of the VIB group element is 15-35 wt% (calculated by oxide), the oxide content of the VIII group element is 2-6.5 wt%, and the phosphorus content of the auxiliary agent is 0-7 wt% (calculated by oxide). The nitrogen content in the coal tar is high, the coal tar exists mainly in the form of heterocyclic compounds, the most main reaction of coal tar hydro-upgrading is aromatic hydrocarbon hydro-saturation, and the main hydrogenation catalyst has excellent aromatic hydrocarbon hydrogenation activity and hydrodenitrogenation activity. The method does not relate to a hydrodesulfurization catalyst and a process, and is not suitable for producing marine fuel oil from raw materials with high sulfur content.
CN109705909a discloses a method for producing marine fuel oil from coal tar. The method comprises the following steps: introducing the dehydrated and mechanically decontaminated coal tar full-fraction raw material into a slurry bed hydrogenation reactor for hydrotreating, and fractionating the effluent of the slurry bed hydrogenation reactor obtained after hydrotreating to obtain marine light fuel oil and marine heavy fuel oil products respectively. Wherein, the carrier of the heterogeneous slurry bed hydrogenation catalyst is active carbon, and Fe and Mo are active components. The method has the limitations of limited desulfurization effect of the hydrotreating catalyst and low yield of low-sulfur fuel oil.
CN110205160a discloses a process method for preparing marine fuel oil by catalytic cracking slurry oil solid removal-hydrogenation. The method comprises the following steps: the oil slurry after the solid removal is hydrogenated under the action of a catalyst taking nickel oxide and molybdenum oxide as active components and aluminum oxide as a carrier to obtain hydrogenated oil slurry, and then the hydrogenated oil slurry is mixed with a ship fuel component to obtain the ship fuel oil. The method can produce the blending components of the marine fuel oil on the basis of lower hydrogen consumption, but still adopts the conventional hydrotreating catalyst, and has the problems of lower desulfurization capacity and low blending proportion.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a hydrodesulfurization catalyst and a preparation method and application thereof. The hydrodesulfurization catalyst is used in the hydrodesulfurization process of a heavy oil fixed bed, can be used for selectively hydrogenating and removing sulfur-containing compounds, can reduce the consumption of hydrogen and save energy, and can be used in the process of producing marine fuel oil by hydrogenating the heavy oil fixed bed.
In a first aspect, the present invention provides a hydrodesulphurisation catalyst comprising: the catalyst comprises a carrier, molybdenum element and VIII group metal element, wherein the molybdenum element exists in the catalyst at least partially in the form of carbonyl molybdenum, and the VIII group metal element exists in the catalyst in the form of VIII group metalloporphyrin compound.
In the hydrodesulfurization catalyst of the present invention, the group VIII metal is contained in an amount of from 0.5% to 8.0%, preferably from 1.0% to 6.0%, based on the weight of the support, and molybdenum is contained in an amount of from 5.0% to 25.0%, preferably from 8.0% to 20.0%, based on the weight of the support.
In the hydrodesulfurization catalyst of the present invention, the molybdenum element is at least partially present in the catalyst in the form of molybdenum carbonyl, and the molybdenum present in the form of molybdenum carbonyl is 40% or more, preferably 50% to 90% by atom of molybdenum, of the total molybdenum.
In the hydrodesulfurization catalyst of the present invention, the form in which molybdenum element is present in the catalyst includes molybdenum carbonyl and molybdenum oxide, the ratio of molybdenum carbonyl to molybdenum oxide being 4 in terms of molybdenum atom: 6-9.5:0.5, preferably 7:3-9:1.
in the hydrodesulfurization catalyst, the VIII metal is at least one selected from nickel and cobalt, and the VIII metalloporphyrin compound is preferably at least one selected from nickel protoporphyrin, cobalt protoporphyrin, nickel tetraphenylporphyrin, cobalt tetraphenylporphyrin, nickel tetramethoxyphenylporphyrin and cobalt tetramethoxyphenylporphyrin.
In the hydrodesulfurization catalyst of the present invention, the carrier may be at least one of alumina, silica, molecular sieve, activated carbon, titanium aluminum, titanium silicon, etc., preferably alumina.
The hydrodesulfurization catalyst of the invention has the following properties: specific surface area of 50-300m 2 Per gram, preferably 100-240m 2 Per g, pore volume is 0.4-1.3mL/g, preferably 0.5-1.0mL/g.
The hydrodesulfurization catalyst of the invention is a fixed bed hydrodesulfurization catalyst.
The hydrodesulfurization catalyst of the present invention is a molded body in the shape of a shape generally used for a fixed bed hydrogenation catalyst, such as a bar, a clover, a sphere, a cylinder, etc., and has a particle size of 2 to 10 mm, preferably 2.5 to 8.0 mm.
In a second aspect, the present invention provides a method for preparing a hydrodesulfurization catalyst comprising:
(1) Preparing a catalyst intermediate containing molybdenum carbonyl;
(2) Impregnating the catalyst intermediate obtained in the step (1) with an organic impregnating solution containing a group VIII metalloporphyrin compound, and removing the organic solvent to obtain the hydrodesulfurization catalyst.
In the step (1), the catalyst intermediate containing molybdenum carbonyl can be prepared by firstly preparing a carrier-supported MoO 3 Is then reacted with MoO 3 At least partially converted to molybdenum carbonyl to produce a catalyst intermediate comprising molybdenum carbonyl.
The preparation of the carrier-loaded MoO 3 The catalyst intermediate of (2) can be prepared by adopting a common method such as a coprecipitation method, an impregnation method, a kneading method and the like, and is preferably prepared by adopting the impregnation method, and the process is as follows: impregnating a molybdenum-containing solution on a carrier, drying and roasting to obtain a carrier-supported MoO 3 Is a catalyst intermediate of (a). Wherein the carrier can be prepared by using commercial products or according to the method disclosed in the prior art. In the molybdenum-containing solution, the solute includes at least one of ammonium molybdate, heteropolyacid salt of molybdenum, and the like. The impregnation method may be either isovolumetric or supersaturated, preferably isovolumetric. The drying conditions are as follows: the drying temperature is 80-180 ℃ and the drying time is 2-6h; the roasting conditions are as follows: the roasting temperature is 400-600 ℃ and the roasting time is 2-5h. The carrier is loaded with MoO 3 The catalyst intermediate of (2) is a molded article, and can be obtainedConventional molding aids, such as peptizers, extrusion aids, and the like, may be added during molding by conventional methods, such as extrusion molding, and the like.
The preparation process of the catalyst intermediate containing molybdenum carbonyl comprises the following steps: moO carried by carrier 3 Mixing the catalyst intermediate with an organic solvent I, a first catalyst and ether gas to make the catalyst intermediate undergo a first reaction, then introducing carbon monoxide into a reaction system to make the catalyst intermediate undergo a second reaction, and drying to obtain the catalyst intermediate containing molybdenum carbonyl. The organic solvent I can be at least one of carbon tetrachloride, trichloropropane, trichloromethane, perchloroethylene and trichloroethylene. The first catalyst can be at least one of iron pentacarbonyl, nickel tetracarbonyl and cobalt octacarbonyl. Organic solvent I and MoO-loaded 3 The mass ratio of the catalyst intermediate is 1:1-5:1, preferably 2:1-4:1. first catalyst and Supported MoO 3 The mass ratio of the catalyst intermediate is 1:10-1:50, preferably 1:20-1:40. the reaction conditions of the first reaction are as follows: the reaction pressure is 1.0-10.0MPa, preferably 3.0-6.0MPa, the reaction temperature is 150-300 ℃, preferably 180-250 ℃, and the reaction time is 1.0-10.0h, preferably 3.0-6.0 h. The ether gas can be one or a mixture of more of diethyl ether and methyl ether. The ether gas is introduced in an amount to maintain the pressure required for the first reaction. The reaction conditions of the second reaction are as follows: the reaction pressure is 5.0-20.0MPa, preferably 8.0-14.0MPa, the reaction temperature is 50-150 ℃, preferably 70-120 ℃, and the reaction time is 1.0-10.0h, preferably 3.0-6.0 h. Wherein the partial pressure of carbon monoxide is more than 50% of the reaction pressure, preferably 60% -80%. The drying conditions are as follows: the drying temperature is 90-150 ℃ and the drying time is 1-4 h.
In the step (2), the preparation method of the organic impregnating solution containing the VIII group metalloporphyrin compound comprises the following steps: the VIII metalloporphyrin compound is dissolved in the organic solvent II. The organic solvent II can be at least one of toluene, benzene, dimethylbenzene, decalin and tetrahydronaphthalene. The group VIII metal compound is derived from at least one soluble salt such as nitrate, citrate, monohydrogen phosphate, dihydrogen phosphate, etc. In the organic impregnating solution containing the VIII metalloporphyrin compound, the concentration of the VIII metalloporphyrin compound is 100g/L-300g/L. The impregnation may be an isovolumetric impregnation method, an unsaturated impregnation method, or the like. The removal of the organic solvent is generally required to be carried out under the condition that the group VIII metalloporphyrin compound is not decomposed, and specifically may be: the temperature is 90-150 ℃ and the time is 1-4 h. The removal of the organic solvent is preferably carried out under reduced pressure.
The hydrodesulfurization catalyst is required to be sulfided before use, and conventional in-situ presulfiding or ex-situ presulfiding can be employed.
The present invention preferably comprises the following vulcanization processes: the hydrodesulfurization catalyst contacts with the vulcanizing liquid and hydrogen for vulcanization, and the vulcanization process is divided into two stages, namely, the first stage: heating to 160-180 ℃, keeping the temperature for 2-6 hours, and in the second stage: heating to 250-320 deg.C, and keeping the temperature for 2-6 hours.
In the vulcanization method, the temperature rising rate of the first stage is 0.5-2.0 ℃ per minute, and the temperature rising rate of the second stage is 1.0-3.0 ℃ per minute.
In the vulcanization method of the present invention, the vulcanizing liquid includes a solvent and a sulfur-containing solute. The mass content of the sulfur-containing solute in the vulcanizing liquid is 1.0% -10.0%, preferably 2.0% -8.0%. The solvent is liquid hydrocarbon. Wherein the liquid hydrocarbon is hydrocarbon with final distillation point not higher than 300 deg.C, and is selected from one or more of saturated alkane with carbon number of 6-10, naphthene with carbon number of 6-10, and distillate oil. The distillate is preferably a low nitrogen distillate having a nitrogen content of not more than 20. Mu.g/g. The sulfur-containing solute has a solubility of more than 10wt% in the solvent at normal temperature and is decomposed with hydrogen to generate H under high temperature condition 2 Sulfur-containing compounds of S, e.g. CS 2 At least one of dimethyl disulfide, dimethyl sulfoxide, tetramethyl sulfoxide, dodecyl sulfide, etc. The amount of sulfiding liquid used is 0.5-6.0 g/h, preferably 1.0-5.0 g/h per gram of catalyst. The hydrogen is hydrogen with purity not lower than 90 v%. The vulcanization conditions are as follows: the hydrogen pressure is 1.0-20.0MPa, preferably 2.0-16.0MPa, and the hydrogen flow rate is 3-20 mL/min, preferably 5-15 mL/min, per gram of catalyst.
The hydrodesulfurization catalyst of the invention can be used for a heavy oil hydrodesulfurization catalyst, in particular for selectively removing sulfur-containing compounds in heavy oil. The heavy oil comprises one or more of catalytic cracking slurry oil, vacuum residuum, coking tower bottom oil, shale oil and deasphalted oil. The sulfur content in the heavy oil is generally not less than 10000. Mu.g/g, and may be 10000 to 40000. Mu.g/g.
The invention also provides application of the hydrodesulfurization catalyst in a process for producing marine fuel oil or marine fuel oil blending component by hydrodesulfurization of a heavy oil fixed bed.
In the present invention, the operation conditions for fixed bed hydrodesulfurization are as follows: the reaction temperature is 320-400 ℃, the reaction pressure is 6.0-25.0 MPa, and the hydrogen oil volume ratio is 200:1-1200:1, liquid hourly space velocity of 0.1-2.0. 2.0h -1 。
Compared with the prior art, the invention has the following advantages:
1. in the hydrodesulfurization catalyst, the active components are mainly in the form of molybdenum carbonyl and a VIII group metalloporphyrin compound in the catalyst, so that the existence state of the active components on a carrier is improved, the action of the active components and the carrier is improved, and the catalyst is favorable for producing a Ni (Co) -Mo-S active phase with high selective desulfurization activity and low aromatic saturation activity after the hydrodesulfurization catalyst is vulcanized. The hydrodesulfurization catalyst is particularly suitable for the fixed bed hydrotreating process of heavy oil, is favorable for selective hydrodesulfurization, reduces the saturation of aromatic hydrocarbon, and has the advantages of low hydrogen consumption and cost reduction, so as to produce low-sulfur marine fuel oil.
2. In the preparation method of the hydrodesulfurization catalyst, molybdenum oxide is firstly loaded on a carrier, at least part of the molybdenum oxide is then converted into molybdenum carbonyl, and then a VIII metalloporphyrin compound is loaded, so that the molybdenum carbonyl forms a framework easy to sulfide, and the VIII metalloporphyrin compound keeps a certain distance between VIII metal atoms, so that the continuous distribution of VIII metal is avoided, a single-point active center is favorably formed in the vulcanization process, the end-to-end adsorption of the catalyst to sulfur-containing compounds is improved, the hydrodesulfurization selectivity of the catalyst is improved, and the saturation selectivity of aromatic hydrocarbon is reduced.
3. The hydrodesulfurization catalyst adopts a low-temperature vulcanization method, is beneficial to effectively dispersing molybdenum carbonyl, firstly forms a molybdenum sulfide frame on the surface of the catalyst, and then distributes the VIII family metal sulfide on the corners of an active phase in a single-point active center mode, so that the hydrodesulfurization catalyst has good selective hydrodesulfurization activity.
4. The heavy oil fixed bed hydrodesulfurization method of the invention adopts the hydrodesulfurization catalyst, has high desulfurization rate and low aromatic saturation rate, can not only produce low-sulfur marine fuel oil, but also save cost, solves the problem of high low-sulfur marine fuel cost produced by adopting the conventional heavy oil fixed bed hydrotreating process in the prior art, and can be directly used in the existing industrialized fixed bed hydrotreating device to produce low-sulfur marine fuel oil.
Detailed Description
The invention is further illustrated below with reference to examples.
In the invention, XPS is measured on a MultiLab 2000 type X-ray photoelectron spectrometer, and the operation conditions are as follows: light source: alkα, E b = 1486.6 eV, and the position of the reference catalyst support Al 2p spectral peak (C1 s,285.0 eV) corrects for charge-induced spectral peak shift. In the invention, the atomic ratio of Mo to VIII on the surface of the sulfided catalyst is measured by XPS method.
In the invention, the specific surface area and pore volume are measured by adopting an ASAP2405 physical adsorption instrument, and the measuring method comprises the following steps: after the sample is treated, liquid N 2 As an adsorbate, the adsorption temperature was-196 ℃ and analytical tests were performed. The specific surface area is calculated by the BET method, and the pore volume and pore distribution are calculated by the BJH method.
Example 1
Weighing 1000.0g of alumina dry rubber powder, adding 20.0g of citric acid and 15.0g of sesbania powder, uniformly mixing, adding 800.0g of aqueous solution containing 2.0% of nitric acid by mass, rolling for 15.0min, and extruding strips by using a clover orifice plate with the diameter of 2.0 mm. Drying at 120 ℃ for 4.0h followed by 600 ℃ firing at 3.0 h. The calcined support was designated S-0.
49.0g of ammonium heptamolybdate and 30.0g of 25wt% strength aqueous ammonia were weighed out to prepare 180mL of an aqueous solution, designated MQ-1. 200. 200g S-0 is impregnated with 180mL MQ-1, dried at 150 ℃ for 3.0h, and then baked at 400 ℃ for 2.0h to obtain the carrier-loaded MoO 3 Is designated MA-1.
50g of MA-1, 150g of carbon tetrachloride and 2.0g of iron pentacarbonyl are weighed into an autoclave with a volume of 500mL, diethyl ether gas is introduced, the pressure is maintained at 4.0MPa, the temperature is 200 ℃, and the reaction is carried out for 5 hours. Then the temperature is reduced to 90 ℃, carbon monoxide is introduced, the pressure is increased to 12.0MPa, the reaction is carried out for 5 hours, the catalyst is taken out, and the catalyst is dried for 2 hours at 120 ℃, so that the catalyst intermediate containing the carbonyl molybdenum is recorded as MT-1.
8.3. 8.3g tetraphenylporphyrin nickel was weighed and dissolved in 50.0mL of toluene, the obtained solution was designated as BQ-1, MT-1 was impregnated with BQ-1, and evaporated under reduced pressure at 120℃for 4.0 hours, and the obtained catalyst was designated as TC-1.
10.0g of TC-1 is taken and filled into a tubular reactor for presulfiding the catalyst, wherein the vulcanized liquid is CS with the mass fraction of 4.0 percent 2 Introducing 30.0mL/h of vulcanizing liquid, 3.0MPa of hydrogen, 120mL/min of hydrogen flow rate, and reacting at the first stage from 120 ℃ at a heating rate of 1.0 ℃ to 160 ℃ for 6.0h at constant temperature; the second stage starts from 160 ℃, the temperature rising rate is 2.0 ℃ per minute, the temperature is kept constant for 2.0 hours after the temperature rises to 280 ℃, and the vulcanization is finished. The catalyst obtained after sulfidation was designated SC-1.
Example 2
Carrier S-0, carrier-supported MoO 3 The procedure of example 1 was followed to prepare catalyst intermediate MA-1.
50. 50gMA-1 g of carbon tetrachloride and 2.0g of iron pentacarbonyl are weighed, added into an autoclave with the volume of 500mL, methyl ether gas is introduced, the pressure is maintained at 4.0MPa, the temperature is 200 ℃, and the reaction is carried out for 5 hours. Then the temperature is reduced to 90 ℃, carbon monoxide is introduced, the pressure is increased to 12.0MPa, the reaction is carried out for 5 hours, the catalyst is taken out, and the catalyst is dried for 2 hours at 120 ℃, so that the catalyst intermediate containing the carbonyl molybdenum is recorded as MT-2.
6.4g of nickel protoporphyrin was weighed and dissolved in 50.0mL of toluene, the resulting solution was designated BQ-2, MT-2 was impregnated with BQ-2, and evaporated under reduced pressure at 120℃for 4.0h, and the resulting catalyst was designated TC-2.
10.0g of TC-2 is taken and filled into a tubular reactor for presulfiding the catalyst, wherein the vulcanized liquid is CS with the mass fraction of 4.0 percent 2 Introducing 30.0mL/h of vulcanizing liquid, 3.0MPa of hydrogen, 120mL/min of hydrogen flow rate, and reacting at the first stage from 120 ℃ at a heating rate of 1.0 ℃ to 160 ℃ for 6.0h at constant temperature; the second stage starts from 160 ℃, the temperature rising rate is 2.0 ℃ per minute, the temperature is kept constant for 2.0 hours after the temperature rises to 280 ℃, and the vulcanization is finished. The catalyst obtained after sulfidation was designated SC-2.
Example 3
Carrier S-0, carrier-supported MoO 3 Catalyst intermediate MA-1 of (C) and catalyst intermediate MT-1 comprising molybdenum carbonyl were prepared in the same manner as in example 1.
8.3g of tetraphenylporphyrin cobalt was weighed and dissolved in 50.0mL of toluene, the resulting solution was designated BQ-3, MT-3 was impregnated with BQ-3, and evaporated under reduced pressure at 120℃for 4.0 hours, and the resulting catalyst was designated TC-3.
10.0g of TC-3 is taken and filled into a tubular reactor for presulfiding the catalyst, wherein the vulcanized liquid is CS with the mass fraction of 4.0 percent 2 Introducing 30.0mL/h of vulcanizing liquid, 3.0MPa of hydrogen, 120mL/min of hydrogen flow rate, and reacting at the first stage from 120 ℃ at a heating rate of 1.0 ℃ to 160 ℃ for 6.0h at constant temperature; the second stage starts from 160 ℃, the temperature rising rate is 2.0 ℃ per minute, the temperature is kept constant for 2.0 hours after the temperature rises to 280 ℃, and the vulcanization is finished. The catalyst obtained after sulfidation was designated SC-3.
Example 4
Carrier S-0, carrier-supported MoO 3 The procedure of example 1 was followed to prepare catalyst intermediate MA-1. The preparation of the catalyst intermediate MT-2 containing molybdenum carbonyl was carried out as in example 2.
10.0g of cobalt tetramethoxyphenylporphyrin was weighed and dissolved in 50.0g of toluene mL, the resulting solution was designated BQ-4, MT-2 was impregnated with BQ-4, and evaporated under reduced pressure at 120℃for 4.0 hours, and the resulting catalyst was designated TC-4.
10.0g of TC-4 is taken and filled into a tubular reactor for presulfiding the catalyst, and the vulcanized liquid is CS with the mass fraction of 4.0 percent 2 Introducing 30.0mL/h of vulcanizing liquid, 3.0MPa of hydrogen, 120mL/min of hydrogen flow rate, and reacting at the first stage from 120 ℃ at a heating rate of 1.0 ℃ to 160 ℃ for 6.0h at constant temperature; the second stage starts from 160 ℃, the temperature rising rate is 2.0 ℃ per minute, the temperature is kept constant for 2.0 hours after the temperature rises to 280 ℃, and the vulcanization is finished. The catalyst obtained after sulfidation was designated SC-4.
Comparative example 1
This comparative example describes the preparation of a conventional nickel molybdenum-alumina catalyst.
Carrier S-0, carrier-supported MoO 3 Catalyst intermediate MA-1 of (C) was prepared as in example 1.
3.5g of nickel nitrate hexahydrate was weighed and dissolved in 50.0mL of water, the resulting solution was designated DQ-1, 50.0g of MA-1 was impregnated with DQ-1, and the resulting catalyst was designated DOC-1 after drying at 150 ℃.
10.0g of DOC-1 is taken and is filled into a tubular reactor for presulfiding the catalyst, and the vulcanized liquid is CS with the mass fraction of 4.0 percent 2 Introducing 30.0mL/h of vulcanizing liquid, 3.0MPa of hydrogen, 120mL/min of hydrogen flow rate, and reacting at the first stage from 120 ℃ at a heating rate of 1.0 ℃ to 160 ℃ for 6.0h at constant temperature; the second stage starts from 160 ℃, the temperature rising rate is 2.0 ℃ per minute, the temperature is kept constant for 2.0 hours after the temperature rises to 280 ℃, and the vulcanization is finished. The catalyst obtained after sulfidation was designated DSC-1.
Comparative example 2
This comparative example describes the preparation of a conventional cobalt molybdenum-alumina catalyst.
Carrier S-0, carrier-supported MoO 3 Catalyst intermediate MA-1 of (C) was prepared as in example 1.
3.5g of cobalt nitrate hexahydrate was weighed and dissolved in 50.0mL of water, the resulting solution was designated DQ-2, 50.0g of MA-1 was impregnated with DQ-2, and the resulting catalyst was designated DOC-2 after drying at 150 ℃.
10.0g of DOC-2 was charged into a tubular reactor to perform catalyst pretreatmentVulcanizing, wherein the vulcanizing liquid is CS with the mass fraction of 4.0% 2 Introducing 30.0mL/h of vulcanizing liquid, 3.0MPa of hydrogen, 120mL/min of hydrogen flow rate, and reacting at the first stage from 120 ℃ at a heating rate of 1.0 ℃ to 160 ℃ for 6.0h at constant temperature; the second stage starts from 160 ℃, the temperature rising rate is 2.0 ℃ per minute, the temperature is kept constant for 2.0 hours after the temperature rises to 280 ℃, and the vulcanization is finished. The catalyst obtained after sulfiding was designated DSC-2.
Comparative example 3
Carrier S-0, carrier-supported MoO 3 Catalyst intermediate MA-1 of (C), and solution BQ-1 were prepared as in example 1.
MA-1 was impregnated with BQ-1 and evaporated under reduced pressure at 120℃for 4.0. 4.0h, the resulting catalyst was designated DOC-3.
10.0g of DOC-3 is taken and is filled into a tubular reactor for presulfiding the catalyst, and the vulcanized liquid is CS with the mass fraction of 4.0 percent 2 Introducing 30.0mL/h of vulcanizing liquid, 3.0MPa of hydrogen, 120mL/min of hydrogen flow rate, and reacting at the first stage from 120 ℃ at a heating rate of 1.0 ℃ to 160 ℃ for 6.0h at constant temperature; the second stage starts from 160 ℃, the temperature rising rate is 2.0 ℃ per minute, the temperature is kept constant for 2.0 hours after the temperature rises to 280 ℃, and the vulcanization is finished. The catalyst obtained after sulfidation was designated DSC-3.
Comparative example 4
Carrier S-0, carrier-supported MoO 3 Catalyst intermediate MA-1 of (C) was prepared as in example 1 and solution BQ-3 was prepared as in example 2.
MA-1 was impregnated with BQ-3 and evaporated at 120℃under reduced pressure for 4.0h, the resulting catalyst was designated DOC-4.
10.0g of DOC-4 is taken and is filled into a tubular reactor to presulfiding the catalyst, wherein the vulcanized liquid is CS with the mass fraction of 4.0 percent 2 Introducing 30.0mL/h of vulcanizing liquid, 3.0MPa of hydrogen, 120mL/min of hydrogen flow rate, and reacting at the first stage from 120 ℃ at a heating rate of 1.0 ℃ to 160 ℃ for 6.0h at constant temperature; the second stage starts from 160 ℃, the temperature rising rate is 2.0 ℃ per minute, the temperature is kept constant for 2.0 hours after the temperature rises to 280 ℃, and the vulcanizing is carried outAnd (5) ending. The catalyst obtained after sulfiding was designated DSC-4.
Comparative example 5
Carrier S-0, carrier-supported MoO 3 Catalyst intermediate MA-1 of (C) and catalyst intermediate MT-1 comprising molybdenum carbonyl were prepared as in example 1, and solution DQ-1 was prepared as in comparative example 1.
MT-1 was impregnated with DQ-1 and evaporated under reduced pressure at 120℃for 4.0h, the resulting catalyst was designated DOC-5.
10.0g of DOC-5 is taken and is filled into a tubular reactor for presulfiding the catalyst, and the vulcanized liquid is CS with the mass fraction of 4.0 percent 2 Introducing 30.0mL/h of vulcanizing liquid, 3.0MPa of hydrogen, 120mL/min of hydrogen flow rate, and reacting at the first stage from 120 ℃ at a heating rate of 1.0 ℃ to 160 ℃ for 6.0h at constant temperature; the second stage starts from 160 ℃, the temperature rising rate is 2.0 ℃ per minute, the temperature is kept constant for 2.0 hours after the temperature rises to 280 ℃, and the vulcanization is finished. The catalyst obtained after sulfidation was designated DSC-5.
Comparative example 6
Carrier S-0, carrier-supported MoO 3 Catalyst intermediate MA-1 of (C) and catalyst intermediate MT-1 comprising molybdenum carbonyl were prepared as in example 1, and solution DQ-2 was prepared as in comparative example 2.
MT-1 was impregnated with DQ-2 and evaporated under reduced pressure at 120℃to give a catalyst designated DOC-6 as 4.0. 4.0 h.
10.0g of DOC-6 is taken and is filled into a tubular reactor for presulfiding the catalyst, and the vulcanized liquid is CS with the mass fraction of 4.0 percent 2 Introducing 30.0mL/h of vulcanizing liquid, 3.0MPa of hydrogen, 120mL/min of hydrogen flow rate, and reacting at the first stage from 120 ℃ at a heating rate of 1.0 ℃ to 160 ℃ for 6.0h at constant temperature; the second stage starts from 160 ℃, the temperature rising rate is 2.0 ℃ per minute, the temperature is kept constant for 2.0 hours after the temperature rises to 280 ℃, and the vulcanization is finished. The catalyst obtained after sulfidation was designated DSC-6.
The catalysts obtained in the above examples and comparative examples were characterized by XPS to obtain the molybdenum carbonyl ratio of molybdenum atoms to total molybdenum, and the results are shown in Table 1. The atomic ratio of Mo to group VIII on the surface of the sulfided catalyst obtained in each of the above examples and comparative examples is shown in table 2.
Table 1 XPS characterization of the catalysts obtained for each example and comparative example
Catalyst numbering Molybdenum carbonyl proportion,% (based on molybdenum atom)
TC-1 83
TC-2 85
TC-3 79
TC-4 82
DOC-1 0
DOC-2 0
DOC-3 0
DOC-4 0
DOC-5 82
DOC-6 83
TABLE 2 atomic ratio of Mo to group VIII on the surfaces of the sulfided catalysts obtained in examples and comparative examples
Catalyst numbering Mo/Co (Ni) atomic ratio
SC-1 6.2
SC-2 6.4
SC-3 6.5
SC-4 6.3
DSC-1 10.4
DSC-2 9.9
DSC-3 8.5
DSC-4 8.4
DSC-5 7.2
DSC-6 7.5
TABLE 3 composition and Properties of the catalysts obtained in examples and comparative examples
Catalyst numbering Co (Ni) content in terms of oxide, wt% Mo content in terms of oxide, wt% Specific surface area, m 2 /g Pore volume, mL/g
TC-1 1.9 16.2 176 0.72
TC-2 1.8 16.0 183 0.73
TC-3 1.8 16.1 179 0.71
TC-4 1.9 16.1 177 0.73
DOC-1 1.8 16.2 182 0.72
DOC-2 1.8 16.1 181 0.74
DOC-3 1.9 16.3 179 0.73
DOC-4 1.9 16.1 174 0.72
DOC-5 1.8 16.1 180 0.70
DOC-6 1.9 16.2 185 0.71
Examples 5 to 8
The catalysts obtained in examples 1 to 4 were evaluated for activity, respectively, and the raw oil was solvent deasphalted oil (properties are shown in Table 4). Filling a hydrogenation protective agent (FZC-100B) and a hydrodemetallization catalyst (FZC-204A) in front of the catalyst by adopting a fixed bed process, wherein the filling volume ratio of the protective agent to the hydrodemetallization catalyst is 1.0:3.0:6.0. the operating conditions are as follows: the reaction temperature is 380 ℃, the reaction pressure is 20.0MPa, and the hydrogen-oil volume ratio is 400:1, liquid hourly space velocity of 0.15. 0.15 h -1 . The analysis results of sulfur, nitrogen and aromatic hydrocarbon contents of the distillate at 180 ℃ or higher in the hydrogenated oil after the reaction was stabilized are shown in Table 5.
Comparative examples 7 to 12
The catalysts obtained in comparative examples 1 to 6 were evaluated for activity, respectively, and the raw oil was solvent deasphalted oil (properties are shown in Table 4). Filling hydrogenation protective agent (FZC-100B) and hydrogenation before the catalyst by adopting a fixed bed processDemetallization catalyst (FZC-204A), the loading volume ratio of the protective agent, hydrodemetallization catalyst and hydrodesulphurisation catalyst being 1.0:3.0:6.0. the operating conditions are as follows: the reaction temperature is 380 ℃, the reaction pressure is 20.0MPa, and the hydrogen-oil volume ratio is 400:1, liquid hourly space velocity of 0.15. 0.15 h -1 . The analysis results of sulfur, nitrogen and aromatic hydrocarbon contents of the distillate at 180 ℃ or higher in the hydrogenated oil after the reaction was stabilized are shown in Table 5.
TABLE 4 Properties of raw oil
Project name Solvent deasphalted oil
Density (15 ℃ C.) kg/m 3 994
Sulfur content, μg/g 24072
Nitrogen content, μg/g 3960
Saturated fraction, wt% 39.8
Fragrance fraction, wt% 49.3
Colloid, wt% 10.9
Carbon residue, wt% 16.6
Table 5 catalyst hydrogenation evaluation results
Desulfurization catalyst numbering Sulfur content, μg/g Nitrogen content, μg/g Fragrance fraction, wt% Carbon residue, wt%
Example 5 SC-1 1232 1469 48 10.0
Example 6 SC-2 1069 1725 45 11.5
Example 7 SC-3 1425 1422 47 10.3
Example 8 SC-4 1160 1754 44 11.8
Comparative example 7 DSC-1 3803 2266 55 7.6
Comparative example 8 DSC-2 3225 2336 53 8.9
Comparative example 9 DSC-3 3522 1850 50 8.2
Comparative example 10 DSC-4 3120 2063 49 9.3
Comparative example 11 DSC-5 2966 1928 58 4.3
Comparative example 12 DSC-6 2854 2199 54 5.4
As can be seen from Table 5, the hydrodesulfurization catalyst of the present invention has excellent hydrodesulfurization and better hydrodenitrogenation properties, and the saturation properties of aromatic hydrocarbons are greatly reduced, which is advantageous for controlling the hydrogen consumption in the hydrogenation process, and is suitable for producing low sulfur marine combustion. Moreover, the catalyst using cobalt porphyrin has stronger hydrodesulfurization performance and lower aromatic hydrocarbon conversion rate than the catalyst using nickel porphyrin.

Claims (26)

1. A hydrodesulfurization catalyst comprising: a support, a molybdenum element and a group VIII metal element, wherein the molybdenum element is present at least partially in the form of molybdenum carbonyl in the catalyst and the group VIII metal element is present in the form of a group VIII metalloporphyrin compound in the catalyst; in the hydrodesulfurization catalyst, the content of the VIII group metal in terms of oxide is 0.5-8.0% and the content of molybdenum in terms of oxide is 5.0-25.0% based on the weight of the carrier; in the hydrodesulfurization catalyst, molybdenum exists in the form of carbonyl molybdenum and accounts for more than 40% of the total molybdenum; in the hydrodesulfurization catalyst, the molybdenum element exists in the catalyst in a form of molybdenum carbonyl and molybdenum oxide, wherein the proportion of the molybdenum carbonyl to the molybdenum oxide is 4:6-9.5:0.5; the properties of the hydrodesulfurization catalyst are as follows: specific surface area of 50-300m 2 Per g, pore volume is 0.4-1.3mL/g.
2. The catalyst of claim 1, wherein: in the hydrodesulfurization catalyst, the content of the VIII group metal in terms of oxide is 1.0-6.0% and the content of the molybdenum in terms of oxide is 8.0-20.0% based on the weight of the carrier.
3. The catalyst according to claim 1 or 2, characterized in that: in the hydrodesulfurization catalyst, molybdenum exists in the form of carbonyl molybdenum and accounts for 50% -90% of the total molybdenum.
4. The catalyst of claim 1, wherein: in the hydrodesulfurization catalyst, the proportion of carbonyl molybdenum to molybdenum oxide in terms of molybdenum atoms is 7:3-9:1.
5. the catalyst of claim 1, wherein: the VIII metal is selected from at least one of nickel and cobalt, and the VIII metalloporphyrin compound is selected from at least one of nickel protoporphyrin, cobalt protoporphyrin, nickel tetraphenylporphyrin, cobalt tetraphenylporphyrin, nickel tetramethoxyphenylporphyrin and cobalt tetramethoxyphenylporphyrin.
6. The catalyst of claim 1, wherein: the carrier is at least one of alumina, silica, molecular sieve, active carbon, titanium aluminum and titanium silicon.
7. The catalyst of claim 1, wherein: the carrier is alumina.
8. The catalyst of claim 1, wherein: the hydrodesulfurization catalyst is a fixed bed hydrodesulfurization catalyst.
9. A process for preparing the catalyst of any one of claims 1-8, comprising:
(1) Preparing a catalyst intermediate containing molybdenum carbonyl;
(2) Impregnating the catalyst intermediate obtained in the step (1) with an organic impregnating solution containing a group VIII metalloporphyrin compound, and removing the organic solvent to obtain the hydrodesulfurization catalyst.
10. The method according to claim 9, wherein: in step (1), a catalyst intermediate containing molybdenum carbonyl is preparedThe process is as follows: firstly, preparing a carrier-loaded MoO 3 Is then reacted with MoO 3 At least partially converted to molybdenum carbonyl to produce a catalyst intermediate comprising molybdenum carbonyl.
11. The method of claim 10, wherein: the preparation of the carrier-loaded MoO 3 The catalyst intermediate of (2) is prepared by adopting an impregnation method, and the process is as follows: impregnating a molybdenum-containing solution on a carrier, drying and roasting to obtain a carrier-supported MoO 3 Is a catalyst intermediate of (a); the drying conditions are as follows: the drying temperature is 80-180 ℃ and the drying time is 2-6h; the roasting conditions are as follows: the roasting temperature is 400-600 ℃, and the roasting time is 2-5h.
12. A method according to claim 10 or 11, characterized in that: the preparation process of the catalyst intermediate containing molybdenum carbonyl comprises the following steps: moO carried by carrier 3 Mixing the catalyst intermediate with an organic solvent I, a first catalyst and ether gas to make the catalyst intermediate undergo a first reaction, then introducing carbon monoxide into a reaction system to make the catalyst intermediate undergo a second reaction, and drying to obtain the catalyst intermediate containing molybdenum carbonyl.
13. The method of claim 12, wherein: the organic solvent I is at least one of carbon tetrachloride, trichloropropane, trichloromethane, perchloroethylene and trichloroethylene; the first catalyst is at least one of iron pentacarbonyl, nickel tetracarbonyl and cobalt octacarbonyl.
14. The method of claim 12, wherein: the organic solvent I and the loaded MoO 3 The mass ratio of the catalyst intermediate is 1:1-5:1, a step of; first catalyst and Supported MoO 3 The mass ratio of the catalyst intermediate is 1:10-1:50.
15. the method of claim 14, wherein: the organic solvent I and the loaded MoO 3 The mass ratio of the catalyst intermediate is 2:1-4:1, a step of; first catalyst and Supported MoO 3 The mass ratio of the catalyst intermediate is 1:20-1:40.
16. the method of claim 12, wherein: the reaction conditions of the first reaction are as follows: the reaction pressure is 1.0-10.0MPa, the reaction temperature is 150-300 ℃ and the reaction time is 1.0-10.0h; the ether gas is one or a mixture of more of diethyl ether and methyl ether; the reaction conditions of the second reaction are as follows: the reaction pressure is 5.0-20.0MPa, the reaction temperature is 50-150 ℃ and the reaction time is 1.0-10.0h; wherein the partial pressure of carbon monoxide accounts for more than 50% of the reaction pressure, and the drying conditions are as follows: the drying temperature is 90-150deg.C, and the drying time is 1-4 h.
17. The method of claim 16, wherein: the reaction conditions of the first reaction are as follows: the reaction pressure is 3.0-6.0MPa, the reaction temperature is 180-250 ℃, and the reaction time is 3.0-6.0h; the reaction conditions of the second reaction are as follows: the reaction pressure is 8.0-14.0MPa, the reaction temperature is 70-120 ℃, and the reaction time is 3.0-6.0 h.
18. The method according to claim 9, wherein: in the step (2), the preparation method of the organic impregnating solution containing the VIII group metalloporphyrin compound comprises the following steps: dissolving a VIII group metalloporphyrin compound in an organic solvent II; the organic solvent II is at least one of toluene, benzene, xylene, decalin and tetrahydronaphthalene; in the organic impregnating solution containing the VIII family metalloporphyrin compound, the concentration of the VIII family metalloporphyrin compound is 100g/L-300g/L; the conditions for removing the organic solvent are as follows: the temperature is 90-150 ℃ and the time is 1-4 h.
19. A method for sulfiding a catalyst according to any one of claims 1 to 8, characterized in that: the vulcanization process comprises the following steps: the hydrodesulfurization catalyst contacts with the vulcanizing liquid and hydrogen for vulcanization, and the vulcanization process is divided into two stages, namely, the first stage: heating to 160-180 ℃, keeping the temperature for 2-6 hours, and in the second stage: heating to 250-320 deg.c and maintaining the temperature for 2-6 hr.
20. The vulcanization process of claim 19, wherein: the temperature rising rate of the first stage is 0.5-2.0 ℃/min, and the temperature rising rate of the second stage is 1.0-3.0 ℃/min.
21. The vulcanization process of claim 19, wherein: the vulcanizing liquid comprises a solvent and a sulfur-containing solute; the mass content of the sulfur-containing solute in the vulcanizing liquid is 1.0-10.0%; the solvent is liquid hydrocarbon; wherein the liquid hydrocarbon is a hydrocarbon with a final boiling point not higher than 300 ℃; the sulfur-containing solute is CS 2 At least one of dimethyl disulfide, dimethyl sulfoxide, tetramethyl sulfoxide and dodecyl sulfide.
22. A vulcanization process as claimed in claim 21, characterized in that: the vulcanizing liquid comprises a solvent and a sulfur-containing solute; the mass content of the sulfur-containing solute in the vulcanizing liquid is 2.0-8.0%.
23. A vulcanization process as claimed in claim 21, characterized in that: the liquid hydrocarbon is one or more of saturated alkane with 6-10 carbon atoms, naphthene with 6-10 carbon atoms and distillate oil.
24. The vulcanization process of claim 19, wherein: the dosage of the vulcanizing liquid is 0.5-6.0 g/h per gram of catalyst; the vulcanization conditions are as follows: the hydrogen pressure is 1.0-20.0MPa, and the hydrogen flow is 3-20 mL/min per gram of catalyst.
25. A vulcanization process as claimed in claim 24, characterized in that: the dosage of the vulcanizing liquid is 1.0-5.0 g/h per gram of catalyst; the vulcanization conditions are as follows: the hydrogen pressure is 2.0-16.0MPa, and the hydrogen flow is 5-15 mL/min per gram of catalyst.
26. Use of the hydrodesulfurization catalyst according to any one of claims 1 to 8 in a process for producing a marine fuel oil or a blending component of a marine fuel oil by fixed bed hydrodesulfurization of a heavy oil.
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