CN107983360B - Catalyst system for preparing fuel oil by shale oil catalytic hydrogenation and use method thereof - Google Patents

Catalyst system for preparing fuel oil by shale oil catalytic hydrogenation and use method thereof Download PDF

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CN107983360B
CN107983360B CN201711194935.8A CN201711194935A CN107983360B CN 107983360 B CN107983360 B CN 107983360B CN 201711194935 A CN201711194935 A CN 201711194935A CN 107983360 B CN107983360 B CN 107983360B
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catalyst
hydrogenation
carrier
metal
active metal
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CN107983360A (en
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罗继刚
陈小斌
张笑剑
柴平平
罗继庆
耿强
梁博
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Liaoning Xinrui Environmental Protection Industry Co ltd
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FUSHUN XINRUI CATALYST CO LTD
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    • B01J35/31—
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/88—Molybdenum
    • B01J23/883—Molybdenum and nickel
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/888—Tungsten
    • B01J23/8885—Tungsten containing also molybdenum
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J35/40—
    • B01J35/615—
    • 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
    • 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
    • C10G45/12—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 crystalline alumino-silicates, e.g. molecular sieves
    • 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
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • B01J2229/183—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself in framework positions
    • 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

Abstract

The application relates to a catalyst system for preparing fuel oil by shale oil catalytic hydrogenation and a using method thereof. The catalyst system comprises a hydrogenation protection catalyst, a hydrofining catalyst and a hydrogenation modification catalyst; the hydrogenation protection catalyst comprises a first carrier, a first active metal and a first auxiliary metal, the hydrofining catalyst comprises a second carrier, a second active metal and a second auxiliary metal, and the hydrogenation modification catalyst comprises a third carrier, a third active metal and a third auxiliary metal; the first carrier and the second carrier are both macroporous alumina, and the third carrier is alumina added with a modified molecular sieve; the first active metal, the second active metal and the third active metal are selected from one or more of W, Mo, Ni and Co in an oxidation state, and the first auxiliary metal, the second auxiliary metal and the third auxiliary metal are selected from one or more of vanadium, zirconium or lanthanide series metals. The catalyst system and the method can effectively solve the problems of coking and catalyst poisoning, and have low cost, safety and stability.

Description

Catalyst system for preparing fuel oil by shale oil catalytic hydrogenation and use method thereof
Technical Field
The invention relates to the field of chemical industry, and particularly relates to a catalyst system for preparing fuel oil by shale oil catalytic hydrogenation and a using method thereof.
Background
Shale oil is a product generated by thermal decomposition of organic matters of oil shale after thermal processing of the oil shale, is similar to natural petroleum, contains more unsaturated hydrocarbons than the natural petroleum, and contains non-hydrocarbon organic compounds such as nitrogen, sulfur, oxygen and the like, and the unsaturated hydrocarbon and the non-hydrocarbon organic compounds are oilThe increase of colloid and the formation of sediment cause the deterioration of stability and the blackening of color. In addition, shale oil contains more inorganic impurities than petroleum. Shale oil is an important component of the energy industry and also a supplementary energy source for natural petroleum. But the high heterocyclic aromatics in shale oil prevent the shale oil from directly acting as transportation fuel; the presence of nitrogen in shale oil reduces fuel stability and storage problems, and also results in increased NO when combustedXThe majority of nitrogen in the shale oil is present as aromatic compounds; high levels of sulfur present in shale oil as SO when the oil is burnedXIs emitted in the form of, and is therefore, an undesirable component. Therefore, the shale oil is used as a raw material to produce the transportation fuel oil, and sulfur and nitrogen are required to be removed, and the content of aromatic hydrocarbon is reduced.
The unit for developing the domestic shale oil deep processing technology is not few, but the shale oil contains more colloid and inorganic impurities than petroleum, so that the processing difficulty of the shale oil is increased, and particularly, the whole fraction processing does not exist for realizing the industrial production at present. The research and development are related in the aspect, but a series of problems exist in the same way.
Unsaturated components in the shale oil react rapidly to generate colloid, and then high-temperature coking blocks a catalyst pore channel or a catalyst bed layer, so that the system pressure difference is increased, the stability of the device is reduced, and even the device is forced to stop working. In addition, shale oil itself is not as stable as crude oil, and thus metastable substances are easily generated in a high-temperature state, and these metastable substances are easily polymerized in a high-temperature and high-pressure hydrogen atmosphere in a reactor, thereby further increasing the coking phenomenon. And colloid and coking can cause the activity of the catalyst to be reduced and even the catalyst to be deactivated. In addition, since the shale oil has a high nitrogen content, 5000-3The relative content of (A) is quite high, so that the acid center of the hydrogenation catalyst is easily damaged, the hydrogenation catalyst is quickly deactivated, the service life is shortened, the production needs to be continuously interrupted to replace the catalyst, and the production cost is high.
In view of this, the present application is specifically made.
Disclosure of Invention
The present application aims to provide a catalyst system for preparing fuel oil by catalytic hydrogenation of shale oil and a use method thereof, so as to solve the above problems.
A catalyst system for preparing fuel oil by shale oil catalytic hydrogenation comprises a hydrogenation protection catalyst, a hydrorefining catalyst and a hydroupgrading catalyst; the hydrogenation protection catalyst comprises a first carrier, a first active metal and a first auxiliary metal, the hydrofining catalyst comprises a second carrier, a second active metal and a second auxiliary metal, and the hydrogenation modification catalyst comprises a third carrier, a third active metal and a third auxiliary metal; the first carrier and the second carrier are both macroporous alumina, and the third carrier is alumina added with a modified molecular sieve; the first active metal, the second active metal and the third active metal are selected from one or more of W, Mo, Ni and Co in an oxidation state, and the first auxiliary metal, the second auxiliary metal and the third auxiliary metal are selected from one or more of vanadium, zirconium or lanthanide series metal.
The carrier, the active metal and the auxiliary metal are selected, so that the catalyst can keep higher catalytic activity in the shale oil raw oil with high nitrogen content, the reaction is ensured to be in a more stable state, the generation of colloid and reaction byproducts is reduced, and the catalyst poisoning is delayed. In addition, the usage amount of the vulcanizing agent can be reduced, so that the sulfur emission is reduced, the environmental pollution and the sewage treatment burden are reduced, and the production cost and the environmental protection pressure are reduced.
Preferably, along the height direction of the hydrogenation protection reactor from top to bottom, the mass content of the first active metal in the hydrogenation protection catalyst is gradually increased within the range of 0-25%, and the mass content of the first auxiliary metal is gradually increased within the range of 0-10%; along the height direction of the hydrofining reactor from top to bottom, the mass content of the second active metal in the hydrofining catalyst is gradually increased within the range of 20-35%, and the mass content of the second auxiliary metal is gradually increased within the range of 4-8%; along the height direction of the hydro-upgrading reactor from top to bottom, the mass content of the third active metal in the hydro-upgrading catalyst is gradually increased within the range of 10-35%, and the mass content of the third auxiliary metal is gradually increased within the range of 4-8%.
The hydrogenation protection reactor, the hydrofining reactor and the hydrogenation modification reactor are sequentially arranged and respectively and correspondingly filled with a hydrogenation protection catalyst, a hydrofining catalyst and a hydrogenation modification catalyst; the advantage of the above arrangement is that the reaction intensity of the material in the reactor is gradually increased with the increase of the content of the active metal (the reaction is more vigorous with the higher content of the active metal); and the reaction is gradual, so that the problems of coking and safety can be effectively solved. It should be noted that the reactor is generally vertically arranged, and the arrangement of the range of the active metal means that a catalyst containing no active metal (having catalytic activity but having very low catalytic activity) or a catalyst containing a trace amount of active metal can be arranged at the topmost end of the reactor.
Further preferably, the porosity of the hydrogenation protection catalyst and the porosity of the hydrorefining catalyst are gradually reduced within the range of 0.5 to 0.8%, and the porosity of the hydroupgrading catalyst is gradually reduced within the range of 0.3 to 0.6% along the flow direction of the reaction material.
The catalyst with large porosity is arranged at the starting end, so that the raw oil can pass substances such as colloid, ash and the like, coking and blockage of a catalyst channel are prevented, the activity of the catalyst is powerfully ensured, the content of the substances is reduced along with the reaction, and the porosity can be properly reduced; second, control of porosity can ensure that the catalyst has optimal catalytic space and location. It is emphasized, however, that the choice of porosity is related to the type of catalyst, the type of active metal, the choice of promoter metal, the bulk density, the support, etc., and is primarily intended to provide a suitable reaction channel for the reaction mass, reduce coking, and increase reaction rates. The porosity is expressed in volume percent.
Optionally, the bulk density of the hydrogenation protection catalyst is 0.4-0.8g/ml, the bulk density of the hydrofining catalyst is 0.5-0.9g/ml, and the bulk density of the hydro-upgrading catalyst is 0.5-0.9 g/ml.
The bulk density is selected so that the catalyst has a proper contact area and space with materials when in use; excessive contact can cause severe reaction, aggravate the occurrence of adverse conditions such as catalyst channel blockage, coking, side reaction increase and the like; too little contact can reduce catalytic activity and reduce production efficiency.
Optionally, the preparation method of the modified molecular sieve comprises the following steps: firstly, carrying out hydrothermal treatment on the molecular sieve at 550-1200 ℃, then soaking the molecular sieve in a solution containing one or more elements of B, Ga, Fe, Cr, Ge, Ti, V and Mn, and finally naturally airing to obtain the modified molecular sieve.
The molecular sieve modification is to make one or more elements of B, Ga, Fe, Cr, Ge, Ti, V and Mn replace part of silicon, aluminum or phosphorus in the molecular sieve to make it become a framework diatomic or polyatomic molecular sieve; the traditional hydrogenation reaction theoretically does not crack oil products into light components, but only generates molecular chain breakage phenomenon in the processes of desulfurization, denitrification and the like, and generates trace components lighter than the raw materials; in the invention, a small amount of modified molecular sieve is added in the hydrogenation modified catalyst, so that some simple chain scission reactions occur in the hydrogenation process of oil products, and the yield of light components is properly improved. Meanwhile, the modified molecular sieve is used as a part of the carrier, which is beneficial to providing a proper reaction site for catalytic reaction, and supplementing, improving and further activating the catalytic efficiency of active metals.
Preferably, the modified molecular sieve accounts for 0.5-20% of the total mass of the third carrier.
The mass percent of the modified molecular sieve in the support is controlled to maintain the beneficial effect on the active metal in a higher range. Experiments show that the overall activity of the catalyst is reduced instead after the proportion of the modified molecular sieve is increased, which proves that the more the elements such as B, Ga, Fe, Cr, Ge, Ti, V, Mn and the like are substituted for silicon, aluminum or phosphorus, the better the elements are, and the elements substituted into the carrier have the synergistic promotion effect and the inhibition effect with the original framework atoms, the active metals and the auxiliary metals.
Preferably, the first carrier and the second carrier are cloverleaf-shaped, hexagonal honeycomb-shaped, raschig ring-shaped, pall ring-shaped or polyhedral hollow sphere-shaped, and the third carrier is cloverleaf-shaped, spherical, gear spherical, quadrangular prism-shaped, porous spherical, cylindrical or raschig ring-shaped.
Further preferably, the first carrier is in the shape of a raschig ring, the second carrier is in the shape of a clover, and the third carrier is in the shape of a cylinder.
The choice of the shape of the different supports is in fact adapted to the position of use, in relation to the activity of the reaction, the temperature, the progress of the reaction, etc. Meanwhile, the first carrier is Raschig ring, the second carrier is clover-shaped, and the third carrier is cylindrical, and the selection is also optimized on the basis of the setting of the content of the active metal and the content of the auxiliary metal.
The application also provides a using method of the catalyst system, and the using conditions of the hydrogenation protection catalyst and the hydrofining catalyst are as follows: the volume space velocity is 0.5-1.0h-1The hydrogen-oil volume ratio is 500-2000, the pressure is 10-20MPa, and the temperature is 130-280 ℃; the reaction conditions of the hydro-upgrading catalyst are as follows: the volume space velocity is 0.3-0.8h-1The volume ratio of hydrogen to oil is 500-2000, the pressure is 10-20MPa, and the temperature is 300-450 ℃.
When the reaction is carried out under the above conditions, the reaction effect is the best. However, the above parameters can be appropriately adjusted as the reactor is enlarged, the throughput is increased, and the quality of the feedstock oil is changed.
Preferably, before use, the whole reaction system needs to be subjected to air exhaust and drying treatment by using inert gas; when in use, a vulcanizing agent is required to be added into the reaction system.
The catalyst system provided by the application needs to be subjected to air exhaust and drying treatment before reaction, and adverse effects of oxygen and water on the reaction system, especially the catalyst, are avoided. Meanwhile, a small amount of vulcanizing agents such as elemental sulfur and the like need to be supplemented, so that the catalytic reaction is ensured to be in a high-efficiency state.
The catalyst system for preparing the fuel oil by the catalytic hydrogenation of the shale oil and the use method thereof can bring at least one of the following beneficial effects:
firstly, the problem of coking is effectively solved, and the effective reaction time is prolonged; secondly, the system stability is high, the whole reaction is carried out in an orderly and stable state, the overall safety is high, and the requirement on the safety performance of equipment is relatively low; thirdly, the catalyst is not easy to be poisoned, the service life is long, the catalytic efficiency is high, frequent shutdown for replacing the catalyst is not needed, and the production cost is reduced; fourthly, the catalytic efficiency is high, the side reaction is less, and the product quality is good; fifthly, the usage amount of the vulcanizing agent is reduced, the sulfur emission is reduced, and the energy conservation and environmental protection are realized.
Detailed Description
The present application will be described in further detail with reference to examples. It is to be understood that the specific embodiments described herein are merely illustrative of the application and are not limiting of the application.
The invention provides a catalyst system for preparing fuel oil by shale oil catalytic hydrogenation, which is characterized in that metastable substances which are easy to react are firstly reacted by a reaction system (the substances are coked at high temperature) through selection of a carrier, active metals and auxiliary metal and control of catalyst filling setting, porosity, bulk density and the like, so that the intensity of the reaction is reduced, and the stable and orderly reaction is ensured; the method solves the defect that a shale oil full-fraction colloid and asphaltene high-hydrogenation device cannot be operated for a long period, simultaneously solves the problems that the shale oil full-fraction has high nitrogen content and low sulfur content, and the activity of the traditional hydrogenation catalyst is quickly lost, ensures the quality and yield of target products, and ensures the long-period production of the device.
The specific process flow is approximately as follows: firstly, a nitrogen or inert gas replacement device is used for carrying out air exhaust treatment on the whole reaction system; the drying treatment of the apparatus and the catalyst is performed simultaneously with the air discharge treatment. Wherein, the gas pressure can be controlled at 1.0-4.0MPa according to the actual situation, and the temperature of the device is controlled at 200-400 ℃. The conditions described above can be adjusted adaptively according to the size of the production scale. Then, after the full-fraction shale oil is subjected to heat exchange by a heat exchanger, impurities with the particle size larger than 20 micrometers are removed by a filter, and then the full-fraction shale oil enters a raw oil buffer tank; under the action of an auxiliary agent pump, outputting a sulfur-containing auxiliary agent (vulcanizing agent) from an auxiliary agent tank, mixing the sulfur-containing auxiliary agent (vulcanizing agent) with shale oil output from a raw oil buffer tank, then exchanging heat through another heat exchanger under the action of a high-pressure feed pump, and then mixing the sulfur-containing auxiliary agent (vulcanizing agent) with hydrogen (the hydrogen comprises two parts, one part is new hydrogen, and the other part is circulating hydrogen separated and recovered from a reaction system) to obtain hydrogen-mixed raw oil; the method comprises the following steps that raw hydrogen-mixed oil enters a hydrogenation protection reactor for reaction, the reaction output of the hydrogenation protection reactor enters a hydrofining reactor for reaction after being heated by a heating furnace, gas-liquid separation is carried out through a first high-pressure separator and a first low-pressure separator after the reaction is finished, the first high-pressure separator carries out primary separation, after the primary separation is finished, the separator at the lower part of the high-pressure separator enters the first low-pressure separator for secondary separation, the separator at the top of the first high-pressure separator enters a circulating hydrogen separating tank for gas-liquid separation, and sulfur-containing sewage is output from the bottom of the first high-pressure separator; separating the material in a low-pressure separator, recovering the top gas (low-pressure gas) separator, sending the bottom liquid separator into a hydro-upgrading reactor for reaction, then carrying out gas-liquid separation through a second high-pressure separator and a second low-pressure separator, and sending the liquid separator at the bottom of the second low-pressure separator into a fractionating tower for fractionation to obtain the final product.
The reaction output is mixed with desalted water and then cooled by an air cooler before entering the first high-pressure separator and the second high-pressure separator; preferably, the heat exchanger can be used for heat exchange before the air cooler cools, so that the effect of optimizing the energy consumption of the reaction system is achieved, and the energy-saving effect is good.
The hydrogenation protection catalyst, the hydrorefining catalyst and the hydroupgrading catalyst are only H in the system2When the concentration of S reaches 50-2000ppm, the activity of the catalyst is in the optimal range; however, the nitrogen content in the raw oil of the shale oil is generally as high as 5000-Reduce H generated by reaction with hydrogen in the system2The S content is far from sufficient, so that the activity of the catalyst is reduced rapidly, therefore, a vulcanizing agent needs to be supplemented in the reaction process, and the vulcanizing agent reacts with hydrogen to generate hydrogen sulfide so as to improve the activity of the catalyst.
A hydrogenation protection catalyst is arranged in the hydrogenation protection reactor, a hydrofining catalyst is arranged in the hydrofining reactor, and a hydrogenation modification catalyst is arranged in the hydrogenation modification reactor; along the height direction of the hydrogenation protection reactor from top to bottom, the mass content of the first active metal in the hydrogenation protection catalyst is gradually increased within the range of 0-25%, and the mass content of the first auxiliary metal is gradually increased within the range of 0-10%; along the height direction of the hydrofining reactor from top to bottom, the mass content of the second active metal in the hydrofining catalyst is gradually increased within the range of 20-35%, and the mass content of the second auxiliary metal is gradually increased within the range of 4-8%; along the height direction of the hydro-upgrading reactor from top to bottom, the mass content of the third active metal in the hydro-upgrading catalyst is gradually increased within the range of 10-35%, and the mass content of the third auxiliary metal is gradually increased within the range of 4-8%. It should be noted that the three-layer catalyst may be free of active metals in the initial stage, primarily for the purpose of preventing coking and preventing transient violent reactions.
The coking is caused because the shale oil has high colloid and asphaltene contents and is easy to coke during reaction; secondly, a carrier of the catalyst is used as a contact medium for reaction, and actually, microchannels of shale oil and hydrogen are arranged on the carrier, the difference of the carriers can cause the difference of the microchannels, the microchannels are not smooth in the reaction, and the shale oil can be accumulated on the catalyst to further block the microchannels, so that not only coking is caused, but also the catalytic efficiency is reduced; thirdly, the reaction temperature and the selection of the active metal of the catalyst and the metal of the auxiliary agent can influence the activity of the reaction, and the rapid coking problem can be caused by the violent reaction; the choice of catalyst is critical to the solution of the coking problem.
The assistant metal is selected mainly because the assistant metal influences the acidity of the catalyst and can change the performance of the catalyst, so that the catalyst can resist the poisoning and interference of N element and has lasting effect; in addition, the inventor finds and analyzes through experiments that: the selected auxiliary agent metal enables the hydrogen pressure in the micro-channel inside the catalyst to be larger than the hydrogen pressure on the outer surface of the catalyst, and the hydrogen has similar adsorption effect, so that the reaction rate on the reaction interface of the micro-channel inside the catalyst is higher than that on the outer surface of the catalyst, and the apparent reaction of the reaction interface is high in overall catalysis efficiency.
The physicochemical properties of the feedstock oil used in the examples of the present application are shown in table 1 below:
TABLE 1 full cut shale oil physico-chemical Properties
Figure BDA0001481775810000091
Figure BDA0001481775810000101
As can be seen from Table 1, the feed oil has high contents of nitrogen, sulfur, carbon residue, ash, colloids, asphaltenes, heavy metals and residual oil, and the feed oil has a nitrogen content much higher than the sulfur content, which increases the difficulty of the hydrogenation of whole shale oil.
The basic requirements of the traditional shale oil hydrogenation catalyst on the raw oil are shown in the following table 2:
TABLE 2 requirement of hydrogenation of conventional shale oil on feed oil
Item Index (I)
Carbon residue/% (m/m) ≦0.05
Colloid/% (m/m) ≦5
Asphaltene/% (m/m) ≦0.02
Dry Point/. degree.C ≦480
Heavy metal content mu g.g-1
Iron ≦2
As can be seen from the data in tables 1 and 2, the content of colloids, asphaltenes, carbon residues and the like in the whole shale oil far exceeds the requirement of the traditional hydrogenation device on the raw material.
In order to clearly illustrate the main physical and chemical indexes of the hydrogenation protection catalyst, the hydrorefining catalyst and the hydroupgrading catalyst, examples 1-2 are specifically selected, and the following tables 3-4 show that:
TABLE 3 Main physicochemical indices of the catalysts in example 1
Figure BDA0001481775810000111
Figure BDA0001481775810000121
TABLE 4 Main physicochemical indices of the catalysts in example 2
Figure BDA0001481775810000122
Figure BDA0001481775810000131
TABLE 5 Main physicochemical indices of the catalysts in example 3
Figure BDA0001481775810000132
Figure BDA0001481775810000141
The first carrier and the second carrier are both macroporous alumina, the third carrier is alumina added with a modified molecular sieve, and the preparation method of the modified molecular sieve comprises the following steps: firstly, carrying out hydrothermal treatment on the molecular sieve at 550-1200 ℃, then soaking the molecular sieve in a solution containing one or more elements of B, Ga, Fe, Cr, Ge, Ti, V and Mn, and finally naturally airing to obtain the modified molecular sieve. In examples 1 to 3, hydrothermal treatment is performed at 550, 900, 1200 ℃, respectively, B is selected in example 1, Ti and V are selected in example 2, Cr, Ge, Mn are selected in example 3, and they can be freely combined and selected for use in other examples, and details are not repeated. The modified molecular sieve accounts for 0.5-20% of the total mass of the third carrier, and in examples 1-3, it accounts for 5%, 10%, and 20%, respectively.
The reactions were carried out according to the methods described above and under the conditions shown in Table 6 below, using the catalytic systems shown in examples 1 to 3.
TABLE 6 Process parameters
Figure BDA0001481775810000142
Figure BDA0001481775810000151
Note: the data are respectively the reaction conditions of the hydrogenation protection catalyst and the hydrogenation refining catalyst (both are consistent) and the reaction conditions of the hydrogenation modification catalyst.
The reaction was carried out under the relevant conditions selected in example 1, and the reaction products were obtained by hydrogenation protection, refining and upgrading, the results of which are shown in table 7 below.
TABLE 7 analysis results of reaction products
Figure BDA0001481775810000152
Figure BDA0001481775810000161
Figure BDA0001481775810000171
The sulfur content of the product obtained in the continuous 15-day reaction process of the raw oil is less than 1 mu g.g-1Nitrogen content less than 5 mu g.g-1The total liquid yield reaches 97 m%, wherein the naphtha fraction accounts for 13 m%, the diesel fraction accounts for 60 m%, and the hydro-upgrading tail oil accounts for 27 m%.
To ensure long-cycle smooth operation of the industrial plant, the present application conducted a life test under the conditions used in example 1. The life evaluation results are shown in Table 8.
TABLE 8 evaluation results of Life test
Figure BDA0001481775810000172
Figure BDA0001481775810000181
Figure BDA0001481775810000191
From table 8, it can be seen that in the life test of >2000h, each index of the hydrogenation product is very stable, which indicates that the method provided by the present application not only has high catalyst activity, but also has good stability, and can completely meet the operation of "long, stable, safe, full, excellent" of industrial devices.
The foregoing examples, as well as the objects of the life test, were all products that were not fractionated. The obtained unfractionated product is sent to a fractionating tower for fractionation to obtain a final product, each product is analyzed, and the analysis results corresponding to the example 1 are shown in the table 9:
TABLE 9 analysis of fractionation results
Figure BDA0001481775810000192
Figure BDA0001481775810000201
As can be seen from the above table, the fraction at <85 ℃ can be used as a low-sulfur solvent oil raw material, the fraction at 85-160 ℃ is a high-quality catalytic reforming raw material, high-octane value motor gasoline can be produced by catalytic reforming, the fraction at 160-370 ℃ can be used as a diesel oil fraction meeting the national V standard, and the fraction at >370 ℃ can be recycled for secondary hydrogenation, so that clean fuel oil can be produced to the maximum extent.
The catalyst system and the use method thereof have the advantages of high catalytic efficiency, low possibility of poisoning of the catalyst, small usage amount of the vulcanizing agent and environmental protection; the coking problem can be effectively solved.
Various modifications and changes may occur to those skilled in the art. Any modification, equivalent replacement, improvement and the like made within the spirit and principle of the present application shall be included in the protection scope of the present application.

Claims (5)

1. A catalyst system for preparing fuel oil by shale oil catalytic hydrogenation is characterized by comprising a hydrogenation protection catalyst, a hydrofining catalyst and a hydrogenation modification catalyst; the hydrogenation protection catalyst comprises a first carrier, a first active metal and a first auxiliary metal, the hydrofining catalyst comprises a second carrier, a second active metal and a second auxiliary metal, and the hydrogenation modification catalyst comprises a third carrier, a third active metal and a third auxiliary metal; the first carrier and the second carrier are both macroporous alumina, and the third carrier is alumina added with a modified molecular sieve; the preparation method of the modified molecular sieve comprises the following steps: firstly, carrying out hydrothermal treatment on the molecular sieve at 550-1200 ℃, then soaking the molecular sieve in a solution containing one or more elements of B, Ga, Fe, Cr, Ge, Ti, V and Mn, and finally naturally airing to obtain the modified molecular sieve; the modified molecular sieve accounts for 0.5-20% of the total mass of the third carrier; the first active metal, the second active metal and the third active metal are selected from one or more of W, Mo, Ni and Co in an oxidation state, and the first auxiliary metal, the second auxiliary metal and the third auxiliary metal are selected from one or more of vanadium, zirconium or lanthanide series metal; along the height direction of the hydrogenation protection reactor from top to bottom, the mass content of the first active metal in the hydrogenation protection catalyst is gradually increased within the range of 0-25%, and the mass content of the first auxiliary metal is gradually increased within the range of 0-10%; along the height direction of the hydrofining reactor from top to bottom, the mass content of the second active metal in the hydrofining catalyst is gradually increased within the range of 20-35%, and the mass content of the second auxiliary metal is gradually increased within the range of 4-8%; along the height direction of the hydro-upgrading reactor from top to bottom, the mass content of the third active metal in the hydro-upgrading catalyst is gradually increased within the range of 10-35%, and the mass content of the third auxiliary metal is gradually increased within the range of 4-8%; along the flowing direction of the reaction materials, the porosity of the hydrogenation protection catalyst and the porosity of the hydrofining catalyst are gradually reduced within the range of 0.5-0.8%, and the porosity of the hydrogenation upgrading catalyst is gradually reduced within the range of 0.3-0.6%; the bulk density of the hydrogenation protection catalyst is 0.4-0.8g/ml, the bulk density of the hydrofining catalyst is 0.5-0.9g/ml, and the bulk density of the hydrogenation upgrading catalyst is 0.5-0.9 g/ml.
2. The catalyst system of claim 1, wherein the first support, the second support are cloverleaf, hexagonal honeycomb, raschig ring, pall ring, or polyhedral hollow sphere, and the third support is cloverleaf, spherical sphere, gear sphere, quadrangular prism, porous sphere, cylindrical, or raschig ring.
3. The catalyst system of claim 2, wherein the first support is a Raschig ring, the second support is a clover-leaf, and the third support is a cylinder.
4. A method for using the catalyst system according to any one of claims 1 to 3, wherein the conditions for using the hydrogenation protection catalyst and the hydrofinishing catalyst are as follows: the volume space velocity is 0.5-1.0h-1The hydrogen-oil volume ratio is 500-2000, the pressure is 10-20MPa, and the temperature is 130-280 ℃, and the reaction conditions of the hydrogenation modification catalyst are as follows: the volume space velocity is 0.3-0.8h-1The volume ratio of hydrogen to oil is 500-2000, the pressure is 10-20MPa, and the temperature is 300-450 ℃.
5. The method of claim 4, wherein the entire reaction system is purged with an inert gas and dried before use; when in use, a vulcanizing agent is required to be added into the reaction system.
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