阅读说明：本技术 一种劣质重油的加工方法及加氢保护催化剂与应用 (Processing method of inferior heavy oil, hydrogenation protection catalyst and application ) 是由 尹宏峰 许杰 于 2019-09-30 设计创作，主要内容包括：本发明公开了一种劣质重油的加工方法及加氢保护催化剂与应用。所述加工方法包括：对劣质重油进行分馏处理,得到重馏分和轻馏分,之后所述重馏分经溶剂抽提得到富芳组分和胶质组分；使所述富芳组分、轻馏分中的萘后馏分均匀混合,并使所获混合物与加氢保护催化剂接触,进行加氢保护反应、加氢精制反应和加氢裂化反应,实现劣质重油的加工；所述加氢保护催化剂包括金属活性组分和载体,所述载体主要由富勒烯的甲苯溶液与浆状氧化铝混合、挤条成型及干燥、焙烧形成,所述金属活性组分包括金属氧化物。本发明的加工方法解决了劣质重油中因沥青质含量高而不能直接采用固定床加氢工艺的问题,使劣质重油全馏分得到充分的利用,提高了劣质重油的综合经济性。(The invention discloses a processing method of inferior heavy oil, a hydrogenation protection catalyst and application. The processing method comprises the following steps: fractionating inferior heavy oil to obtain heavy fraction and light fraction, and extracting the heavy fraction with solvent to obtain aromatic-rich component and colloid component; uniformly mixing the aromatic-rich component and the naphthalene later fraction in the light fraction, and contacting the obtained mixture with a hydrogenation protection catalyst to perform hydrogenation protection reaction, hydrogenation refining reaction and hydrocracking reaction, thereby realizing the processing of inferior heavy oil; the hydrogenation protection catalyst comprises a metal active component and a carrier, wherein the carrier is mainly formed by mixing a toluene solution of fullerene with slurry-like alumina, extruding, forming, drying and roasting, and the metal active component comprises metal oxide. The processing method solves the problem that the fixed bed hydrogenation process cannot be directly adopted due to high asphaltene content in the inferior heavy oil, fully utilizes the whole fraction of the inferior heavy oil, and improves the comprehensive economy of the inferior heavy oil.)

1. A method for processing inferior heavy oil is characterized by comprising the following steps:

fractionating inferior heavy oil to obtain heavy fraction and light fraction, and extracting the heavy fraction with solvent to obtain aromatic-rich component and colloid component;

uniformly mixing the aromatic-rich component and the naphthalene later fraction in the light fraction, and contacting the obtained mixture with a hydrogenation protection catalyst to perform hydrogenation protection reaction, hydrogenation refining reaction and hydrocracking reaction, thereby realizing the processing of inferior heavy oil;

the hydrogenation protection catalyst comprises a metal active component and a carrier loaded with the metal active component, wherein the carrier is mainly prepared by mixing and extruding a toluene solution of fullerene and slurry-like alumina at a speed of 2-5 g/sForming, drying and roasting the strips to form the metal active component, wherein the metal active component comprises metal oxide, and the metal oxide comprises oxides of VIB group and/or VIII group metal elements; the specific surface area of the hydrogenation protection catalyst is 250-300 m²The average pore diameter is 30-50 nm, wherein the pore passage with the diameter of 10-100 nm accounts for 40-70%.

2. The method of claim 1, wherein the method comprises: distilling the rich aromatic component, removing the solvent to obtain a net rich aromatic component, and then uniformly mixing the net rich aromatic component with the naphthalene post-fraction in the light fraction; and/or the cutting points of light fractions and heavy fractions contained in the inferior heavy oil are 220-230 ℃;

and/or, the conditions for solvent extraction of the heavy fraction comprise: the mass ratio of the solvent to the heavy fraction is 1.0-3.0: 1, the temperature is 50-70 ℃; preferably, the solvent comprises a benzene compound, preferably benzene and/or toluene.

3. The method of claim 1, wherein the method comprises: filling the hydrogenation protection catalyst in a hydrogenation protection reaction area, filling a hydrofining catalyst in a hydrofining reaction area, filling a hydrofining catalyst in the upstream of a hydrocracking reaction area, and filling a hydrocracking catalyst in the downstream; preferably, the volume ratio of the hydrofining catalyst to the hydrocracking catalyst is 5-50: 100, respectively; preferably, the volume ratio of the volume of the hydrogenation protection catalyst to the volume of the hydrocracking catalyst is 20-70: 100.

4. the method of claim 3 wherein the processing of the inferior heavy oil comprises: the operation conditions of the hydrogenation protection reaction zone and the hydrogenation refining reaction zone are as follows: the reaction temperature is 340-380 ℃, the hydrogen partial pressure is 12.0-14.0 MPa, and the volume ratio of hydrogen to oil is 1000: 1-1400: 1, the liquid hourly space velocity is 0.5-1.0 h^-1(ii) a And/or the operating conditions of the hydrocracking reaction zone are as follows: the reaction temperature is 360-380 ℃, the hydrogen partial pressure is 12.0-14.0 MPa, and the volume of hydrogen oilThe ratio is 1000: 1-1400: 1, the liquid hourly space velocity is 0.3-0.7 h^-1。

5. The method of claim 1, wherein the method further comprises the steps of: the hydrogenation protection catalyst comprises 70-96 wt% of a carrier and 1-10 wt% of a metal oxide;

and/or the VIB group metal oxide is selected from molybdenum trioxide and/or tungsten trioxide, and the content of the metal oxide in the hydrogenation protection catalyst is 1-4 wt%; and/or the VIII group metal oxide is selected from nickel oxide and/or cobalt oxide, and the content of the metal oxide in the hydrogenation protection catalyst is 1-6 wt%.

6. The method of claim 1, wherein the carrier is prepared by a method comprising: firstly, mixing alumina and a toluene solution of fullerene, adding an extrusion aid, extruding into strips, forming, and then drying and roasting; preferably, the amount of the fullerene is 0.1-0.6 wt% of the total mass of the carrier, and particularly preferably 0.2-0.5 wt%; preferably, the fullerene is formed by dissolving toluene; particularly preferably, the mass ratio of toluene to fullerene used for dissolving toluene is 200-350: 1, the dissolving temperature is 20-40 ℃, the pressure is 0.10-0.25 MPa, and the dissolving time is 3-10 min; particularly preferably, C60 fullerene powder is adopted as the fullerene, and the purity is more than or equal to 99.5 wt%; preferably, the preparation method comprises the following steps: toluene and alumina are mixed and stirred to form the slurry alumina; particularly preferably, the mass ratio of the alumina to the toluene is 3-6: 1; particularly preferably, the pore volume of the alumina is 1.1-1.6 cm³(ii)/g, the average pore diameter is 10 to 20 nm.

7. A preparation method of a hydrogenation protection catalyst is characterized by comprising the following steps:

1) dissolving fullerene in toluene to obtain fullerene solution;

2) mixing alumina and toluene to form slurry alumina, wherein the mass ratio of the alumina to the toluene is (3-6): 1;

3) adding the fullerene solution obtained in the step 1) into the slurry-like alumina obtained in the step 2) at a dropping rate of 2-5 g/sec, uniformly mixing, extruding into strips, forming, and then drying and roasting to obtain a carrier;

4) adding a nonionic surfactant into an aqueous solution of a water-soluble compound corresponding to a metal active component precursor to form a mixed solution, wherein the metal active component precursor is selected from water-soluble compounds containing VIB group and/or VIII group metal elements, and the metal active component is selected from metal oxides, then soaking the carrier obtained in the step 3) into the mixed solution, and then drying and roasting to obtain the hydrogenation protection catalyst.

8. The method of claim 7, wherein: in the step 1), the fullerene is dissolved in toluene for treatment, the dissolving temperature is 20-40 ℃, the pressure is 0.10-0.25 MPa, the dissolving time is 3-10 min, and the mass ratio of the toluene and the fullerene used for toluene dissolution is 200-350: 1;

and/or, the step 3) comprises: adding an extrusion aid in the process of mixing the slurry alumina and the fullerene solution, extruding strips for forming, and then drying and roasting; preferably, the temperature of the drying treatment is 120-160 ℃; preferably, the roasting treatment temperature is 450-700 ℃, and the roasting time is 1-15 h;

and/or the drying temperature adopted in the step 4) is 80-150 ℃, the roasting temperature is 400-650 ℃, and the roasting time is 1-15 h;

and/or the VIB group or VIII group metal element is selected from any one or the combination of more than two of molybdenum, tungsten, cobalt and nickel; and/or the metal oxide comprises any one or the combination of more than two of molybdenum trioxide, tungsten trioxide, nickel oxide and cobalt oxide; and/or the water-soluble compound corresponding to the metal active component comprises any one or the combination of more than two of ammonium molybdate, ammonium metatungstate, nickel nitrate, basic nickel carbonate, cobalt nitrate and cobalt acetate;

and/or the pore volume of the alumina is 1.1-1.6 cm³(ii)/g, the average pore diameter is 10-20 nm;

and/or the amount of the fullerene is 0.1-0.6 wt% of the total mass of the carrier, preferably 0.2-0.5 wt%; preferably, the fullerene is C60 fullerene powder, and the purity is more than or equal to 99.5 wt%;

and/or the dosage of the nonionic surfactant is 2-8 wt% of the total mass of the carrier; preferably, the nonionic surfactant is fatty alcohol polyether.

9. The hydrogenation protection catalyst prepared by the method of any one of claims 7 to 8, which has an average pore diameter of 30 to 50nm, wherein pores with a diameter of 10 to 100nm account for 40 to 70%, and a specific surface area of 250 to 300m²And/g, and comprises 70 to 96 wt% of a carrier, 1 to 10 wt% of a metal oxide.

10. Use of the hydrogenation protection catalyst of claim 9 in the hydroprocessing of low grade heavy oils; preferably, the low-quality heavy oil comprises coker diesel oil, catalytic diesel oil, coker gas oil, vacuum residuum, ethylene tar, catalytically cracked cycle oil, catalytically cracked oil slurry, heavy distillate oil obtained by coal liquefaction, coal gasification or coal coking, and is preferably coal liquefied diesel oil, wax oil, residuum fraction, anthracene oil or soft asphalt.

Technical Field

The invention relates to a processing method of inferior heavy oil, in particular to a method for treating inferior heavy oil by using a distillation, crystallization and fixed bed hydrogenation combined process, a hydrogenation protection catalyst used by the method, and a preparation method and application of the hydrogenation protection catalyst.

Background

The increasing shortage of petroleum resources and the non-regenerability thereof make emission reduction and efficiency improvement of refineries necessary. Poor heavy oil such as ethylene tar and catalytic slurry oil is mainly sold as heavy fuel oil or partially used as carbon black raw material at present, and the added value is low. The heavy oil has high content of impurities such as carbon residue, asphaltene and metal, can not be directly used as a fixed bed hydrogenation device, and needs to be separated or intercepted, if the impurities can not be effectively removed, the impurities can generate adverse effects on the activity of a downstream main catalyst, namely a hydrofining catalyst and a hydrocracking catalyst, on one hand, the main catalyst is inactivated or the service life of the main catalyst is shortened due to the blockage of the orifice of the main catalyst; on the other hand, the pressure drop of the main catalyst bed layer is increased, so that the industrial operation device is frequently shut down or the catalyst is replaced, and the two aspects seriously affect the economical efficiency of the hydrotreating industrial device.

In order to improve the economic benefit of the inferior heavy oil, various related enterprises develop various comprehensive utilization methods. For example, patent publication No. CN1970688A discloses a method in which a light fraction having a boiling point of 260 to 280 ℃ is cut out from ethylene tar, unsaturated hydrocarbons in the light fraction are removed by a hydrofining method, and then naphthalene and methylnaphthalene products are extracted from the light fraction, with a small amount of solvent naphtha product being by-produced. The method only utilizes light fractions which account for little proportion in the inferior heavy oil, and over 80 percent of the inferior heavy oil fractions are not effectively treated; meanwhile, the provided hydrofining conditions can not treat inferior heavy oil fractions with the boiling point higher than 280 ℃. In addition, the methods disclosed in the patent publication nos. CN103805248A, CN102234538A, CN103102978A, CN101724448A and CN109929592A have different process routes, and these methods have problems of complicated processing flow, high production cost and the like.

The poor-quality heavy oil is produced into high-added-value products by adopting a fixed bed hydrotreating process, and how to prepare a hydrogenation protection catalyst with strong scale capacity and good activity stability is a subject of attention in the field of catalytic research. In the case of a supported catalyst, although the carrier does not have direct catalytic activity in some cases, the active component can stably exert its catalytic performance only by being supported on an appropriate carrier, and a catalyst having a high degree of dispersion can be prepared by using a carrier having a high specific surface, thereby improving the reaction performance of the catalyst. The catalyst has larger pore volume, so that the coking resistance or carbon deposit resistance of the catalyst can be improved, and the service life of the catalyst is prolonged.

CN1107102C selects sesbania powder or carbon black and other substances as pore-enlarging agents, which can reduce the mechanical strength of the prepared hydrogenation protection catalyst. CN101890381B is prepared by a rodlike nanometer oxide carrier, macropores in pore distribution account for a large proportion of pore volume, pore channels above 1000nm contain more than 36%, and the demetallization rate of the hydrogenation protection catalyst is lower by about 48%. The hydrogenation protection catalyst disclosed in CN102989491A has a pore volume of 0.98-1.15 ml/g and a specific surface area of 340-380 m²The demetallization rate of the catalyst is 70-78 percent and is low.

Disclosure of Invention

The invention mainly aims to provide a processing method of inferior heavy oil with high added value of products and high utilization rate of inferior heavy oil, so as to overcome the defects in the prior art.

The invention also aims to provide a hydrogenation protection catalyst used in the processing method and a preparation method and application thereof.

In order to achieve the purpose, the technical scheme adopted by the invention comprises the following steps:

the embodiment of the invention provides a processing method of inferior heavy oil, which comprises the following steps:

fractionating inferior heavy oil to obtain heavy fraction and light fraction, and extracting the heavy fraction with solvent to obtain aromatic-rich component and colloid component;

uniformly mixing the aromatic-rich component and the naphthalene later fraction in the light fraction, and contacting the obtained mixture with a hydrogenation protection catalyst to perform hydrogenation protection reaction, hydrogenation refining reaction and hydrocracking reaction, thereby realizing the processing of inferior heavy oil;

the hydrogenation protection catalyst comprises a metal active component and a carrier loading the metal active component, wherein the carrier is mainly formed by mixing a toluene solution of fullerene with slurry-like alumina at the speed of 2-5 g/s, extruding, forming, drying and roasting, the metal active component comprises a metal oxide, and the metal oxide comprises an oxide of a VIB group and/or VIII group metal element; the specific surface area of the hydrogenation protection catalyst is 250-300 m²The average pore diameter is 30-50 nm, wherein the pore passage with the diameter of 10-100 nm accounts for 40-70%.

The embodiment of the invention also provides a preparation method of the hydrogenation protection catalyst, which comprises the following steps:

1) dissolving fullerene in toluene to obtain fullerene solution;

2) mixing alumina and toluene to form slurry alumina, wherein the mass ratio of the alumina to the toluene is (3-6): 1;

3) adding the fullerene solution obtained in the step 1) into the slurry-like alumina obtained in the step 2) at a dropping rate of 2-5 g/sec, uniformly mixing, extruding into strips, forming, and then drying and roasting to obtain a carrier;

4) adding a nonionic surfactant into an aqueous solution of a water-soluble compound corresponding to a metal active component precursor to form a mixed solution, wherein the metal active component precursor is selected from water-soluble compounds containing VIB group and/or VIII group metal elements, and the metal active component is selected from metal oxides, then soaking the carrier obtained in the step 3) into the mixed solution, and then drying and roasting to obtain the hydrogenation protection catalyst.

The embodiment of the invention also provides a hydrogenation protection catalyst prepared by the method, the average pore diameter of the hydrogenation protection catalyst is 30-50 nm, the pore channels with the diameters of 10-100 nm account for 40-70%, and the specific surface area is 250-300 m²And/g, and comprises 70 to 96 wt% of a carrier, 1 to 10 wt% of a metal oxide.

The embodiment of the invention also provides application of the hydrogenation protection catalyst in the hydrogenation treatment of inferior heavy oil.

Compared with the prior art, the method for treating the inferior heavy oil has the following advantages:

1) the processing method of the inferior heavy oil selects a proper cutting point to fractionate the whole fraction of the inferior heavy oil, the fraction with high naphthalene content is separated, crude naphthalene products are obtained through rectification and crystallization, the naphthalene back fraction and the net aromatic-rich component are mixed together to be used as the feeding material of a fixed bed hydrogenation device, and heavier colloid components are used as carbon material raw materials. On one hand, asphaltene and carbon residue which are easy to cause the inactivation of the fixed bed hydrogenation catalyst are separated out, and the high-quality feeding of the fixed bed hydrogenation device is obtained; on the other hand, the utilization rate of the inferior heavy oil is obviously improved, high added-value products such as naphthalene, clean fuel oil and the like can be obtained, and the comprehensive economy of the inferior heavy oil is improved;

2) the processing method of the inferior heavy oil provided by the invention adopts a combined process of distillation, crystallization, extraction and fixed bed hydrogenation, and converts the inferior heavy oil which needs to be processed by a fluidized bed and slurry bed hydrogenation process into high-added-value products such as naphthalene, carbon material raw materials, clean fuel oil and the like, so that the equipment investment is remarkably reduced, and the processing method is beneficial to emission reduction and synergy of a refinery;

3) according to the invention, tail oil circulation and heavy fraction mixing are adopted as raw materials of the extraction process, so that the conversion rate of the raw materials can be improved, the yield of products with high added values is increased, and the method is also beneficial to relieving the temperature rise of a hydrogenation reactor bed layer;

4) the preparation method of the hydrogenation protection catalyst provided by the invention adopts fullerene as a pore-enlarging agent, and has the double effects of enlarging pores and increasing the strength of the catalyst. The catalyst has the advantages of good activity, high strength, reasonable pore distribution, strong metal capacity, more uniform dispersion of active components and good activity stability, and is suitable for being used as a hydrogenation protection catalyst for an inferior heavy oil fixed bed;

5) the method solves the problem that the inferior heavy oil cannot be directly used as the feeding material of the fixed bed hydrogenation device due to high asphaltene content, fully utilizes the whole fraction of the inferior heavy oil, and improves the comprehensive economy of the inferior heavy oil.

Drawings

In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments described in the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.

Fig. 1 is a schematic view of a process for processing inferior heavy oil according to an exemplary embodiment of the present invention.

Description of the drawings: 1-inferior heavy oil, 2-distillation, 3-light fraction, 4-heavy fraction, 5-crystallization, 6-cooling, 7-naphthalene product, 8-naphthalene after fraction, 9-extraction, 10-standing, 11-aromatic-rich component, 12-colloid component, 13-benzene solvent, 14-distillation, 15-clean aromatic-rich component, 16-hydrofining reaction unit, 17-hydrocracking unit, 18-distillation, 19-gas product, 20-gasoline, 21-diesel oil, 22-tail oil and 23-new hydrogen.

Detailed Description

In view of the deficiencies in the prior art, the inventors of the present invention have made extensive studies and practice to provide a technical solution of the present invention, which mainly provides a method for processing inferior heavy oil, comprising: fractionating inferior heavy oil into light fraction and heavy fraction, extracting the heavy fraction by a solvent to obtain an aromatic-rich component and a colloid component, distilling the aromatic-rich component out of the solvent to obtain an aromatic-rich component, mixing the aromatic-rich component with the naphthalene fraction obtained by separating the light fraction, introducing the mixture into a hydrogenation reaction zone, sequentially passing through a hydrogenation protection reaction zone, a hydrogenation refining reaction zone and a hydrocracking reaction zone for hydrogenation reaction, separating the obtained hydrogenation product to obtain products such as gas, gasoline, diesel oil, tail oil and the like, and mixing the tail oil with the heavy fraction to restart new reaction.

The technical solution, its implementation and principles, etc. will be further explained as follows.

One aspect of the embodiments of the present invention provides a method for processing inferior heavy oil, which includes:

fractionating inferior heavy oil to obtain heavy fraction and light fraction, and extracting the heavy fraction with solvent to obtain aromatic-rich component and colloid component;

uniformly mixing the aromatic-rich component and the naphthalene later fraction in the light fraction, and contacting the obtained mixture with a hydrogenation protection catalyst to perform hydrogenation protection reaction, hydrogenation refining reaction and hydrocracking reaction, thereby realizing the processing of inferior heavy oil;

the hydrogenation protection catalyst comprises a metal active component and a carrier loading the metal active component, wherein the carrier is mainly formed by mixing a toluene solution of fullerene with slurry-like alumina at the speed of 2-5 g/s, extruding, forming, drying and roasting, the metal active component comprises a metal oxide, and the metal oxide comprises an oxide of a VIB group and/or VIII group metal element; the specific surface area of the hydrogenation protection catalyst is 250-300 m²The average pore diameter is 30-50 nm, wherein the pore passage with the diameter of 10-100 nm accounts for 40-70%.

In some embodiments, the method for processing inferior heavy oil comprises: distilling the rich aromatic component, removing the solvent to obtain a net rich aromatic component, and then uniformly mixing the net rich aromatic component with the naphthalene after-fraction in the light fraction.

In some embodiments, the inferior heavy oil comprises a cut point of light fraction and heavy fraction of 220 to 230 ℃.

In some embodiments, the conditions under which the heavy fraction is subjected to solvent extraction include: the mass ratio of the solvent to the heavy fraction is 1.0-3.0: 1, the temperature is 50-70 ℃.

Further, the solvent includes benzene compounds, preferably benzene, toluene, etc., but is not limited thereto.

In the method of the present invention, the colloidal component may be used as a carbon fiber pitch feedstock. Compared with the inferior heavy oil, the heavy fraction obtained by solvent extraction of the inferior heavy oil has the advantages of removing light fraction, increasing the content of aromatic hydrocarbon, increasing C/H and improving the softening point, and solves the problem that the whole fraction of the inferior heavy oil has too low softening point and can be used as carbon fiber asphalt only by preparing a large amount of components with high softening point, so the inferior heavy oil can be used as an ideal raw material of general asphalt-based carbon fiber.

In some embodiments, the method for processing inferior heavy oil comprises:

and filling the hydrogenation protection catalyst in the hydrogenation protection reaction area, filling the hydrofining catalyst in the hydrofining reaction area, filling the hydrofining catalyst in the upstream of the hydrocracking reaction area, and filling the hydrocracking catalyst in the downstream.

Further, the volume ratio of the hydrofining catalyst to the hydrocracking catalyst is 5-50: 100, i.e. the hydrofinishing catalyst used is 5% to 50% of the loading volume of the hydrocracking catalyst.

Further, the volume ratio of the volume of the hydrogenation protection catalyst to the volume of the hydrocracking catalyst is 20-70: 100, i.e. the hydrogenation protection catalyst accounts for 20-70% of the volume of the hydrocracking catalyst.

In some embodiments, the operating conditions of the hydroprocessing reaction zone are the same as the operating conditions of the hydrofinishing reaction zone, i.e., the operating conditions of both the hydroprocessing reaction zone and the hydrofinishing reaction zone are: the reaction temperature is 340-380 ℃, the hydrogen partial pressure is 12.0-14.0 MPa, and the volume ratio of hydrogen to oil is 1000: 1-1400: 1, the liquid hourly space velocity is 0.5-1.0 h^-1。

In some embodiments, the operating conditions of the hydrocracking reaction zone are: the reaction temperature is 360-380 ℃, the hydrogen partial pressure is 12.0-14.0 MPa, and the volume ratio of hydrogen to oil is 1000: 1-1400: 1, the liquid hourly space velocity is 0.3-0.7 h^-1。

In the method, the hydrogenation reaction zone can adopt a one-section series process, namely, the hydrofining reaction zone and the hydrocracking reaction zone adopt a one-section series process, and the two reaction zones can be in the same reactor or different reactors respectively. The clean fuel oil fraction yield is high by adopting a one-stage series process, and the method has the advantage of low investment compared with a hydrogenation process.

In the method, the hydrofining catalyst can adopt a fixed bed hydrofining catalyst commonly used in the commercial petrochemical industry, and the hydrocracking catalyst can adopt a fixed bed hydrocracking catalyst commonly used in the commercial petrochemical industry.

In the method, the net aromatic-rich component and the naphthalene after-fraction enter a hydrogenation reaction zone together, contact with a hydrogenation protection catalyst firstly, and mainly remove impurities and partial carbon residue in the hydrogenation protection catalyst so as to avoid coking of the downstream hydrogenation catalyst and prolong the running period of the device.

In some embodiments, the hydrogenation protection catalyst comprises 70 to 96 wt% support, 1 to 10 wt% metal oxide.

In some embodiments, the group VIB metal oxide is selected from molybdenum trioxide and/or tungsten trioxide, and the amount of metal oxide in the hydrogenation protection catalyst is from 1 to 4 wt%.

Further, the VIII group metal oxide is selected from nickel oxide and/or cobalt oxide, and the content of the metal oxide in the hydrogenation protection catalyst is 1-6 wt%.

In some embodiments, the method of making the carrier comprises: firstly, mixing alumina and a toluene solution of fullerene, adding an extrusion aid, extruding and forming, and then drying and roasting.

Furthermore, the amount of the fullerene is 0.1-0.6 wt%, preferably 0.2-0.5 wt% of the total mass of the carrier.

Further, the fullerene is formed by dissolving fullerene in toluene.

In the catalyst, the fullerene in the carrier is dissolved by toluene before being mixed with alumina, wherein the toluene is dissolved at the temperature of 20-40 ℃ under the pressure of 0.10-0.25 MPa for 3-10 min; the mass ratio of toluene and fullerene adopted for toluene dissolution is 200-350: 1.

furthermore, the fullerene is C60 fullerene powder, and the purity is more than or equal to 99.5 wt%.

Further, the preparation method comprises the following steps: toluene and alumina are mixed and stirred to form the slurry alumina. The alumina was first slurried with a small amount of toluene. Further, the fullerene toluene solution is mixed with the slurry alumina at a rate of 2 to 5 g/sec. In the preparation process of the hydrogenation protection catalyst provided by the invention, the slurry-like alumina is mixed with the fullerene toluene solution at a certain dropping speed, so that the fullerene and the alumina can be mixed more uniformly, and the preparation method is beneficial to fullerene modified carriers.

In some embodiments, the method of making the carrier comprises: firstly, mixing alumina and a toluene solution of fullerene, adding an extrusion aid, extruding and forming, and then drying and roasting.

Further, the temperature of the drying treatment is 120-160 ℃.

Further, the roasting treatment temperature is 450-700 ℃, and the roasting time is 1-15 h.

In some embodiments, in the catalyst of the present invention, the alumina has a pore volume of 1.1 to 1.6cm³(ii)/g, the average pore diameter is 10 to 20 nm.

The hydrogenation protection catalyst provided by the invention adopts fullerene C60 with a very small particle size, the molecules of the fullerene C60 are in a football shape, the diameter of the fullerene C60 is only 0.7nm, and the fullerene can be easily combined with an alumina carrier after being dissolved in toluene, so that the pore volume and the specific surface area of the alumina carrier with the average pore diameter of 10-20 nm are further increased. Therefore, the particle size of the fullerene C60 is small, the addition amount of the fullerene C60 to the alumina carrier is small and is less than 1%, and the pore distribution of the catalyst is not diffused due to the generation of a large amount of gas in the roasting process. Only coherent pore canals with consistent orifices and pore canals are formed, so that the metal capacity of the catalyst is enhanced; meanwhile, due to the excellent strength and hardness of the fullerene C60, the strength of the prepared catalyst is not damaged like other physical pore-expanding agents, and the double effects of expanding pores and increasing the strength are achieved.

Another aspect of an embodiment of the present invention provides a method for preparing a hydrogenation protection catalyst, including:

1) dissolving fullerene in toluene to obtain fullerene solution;

2) mixing alumina and toluene to form slurry alumina, wherein the mass ratio of the alumina to the toluene is (3-6): 1;

3) adding the fullerene solution obtained in the step 1) into the slurry-like alumina obtained in the step 2) at a dropping rate of 2-5 g/sec, uniformly mixing, extruding into strips, forming, and then drying and roasting to obtain a carrier;

4) adding a nonionic surfactant into an aqueous solution of a water-soluble compound corresponding to a metal active component precursor to form a mixed solution, wherein the metal active component precursor is selected from water-soluble compounds containing VIB group and/or VIII group metal elements, and the metal active component is selected from metal oxides, then soaking the carrier obtained in the step 3) into the mixed solution, and then drying and roasting to obtain the hydrogenation protection catalyst.

The method for adding the fullerene in the preparation process of the hydrogenation protection catalyst provided by the invention can lead another factor of good activity and stability of the obtained catalyst to be possibly related to that the fullerene C60 can form coordination compounds with metals in VIII families such as Ni, osmium and the like.

In the present invention, the fullerene is added to make the active component loaded on the carrier disperse more uniformly than the catalyst prepared by adding common physical pore-enlarging agent such as carbon black, because the fullerene C60 is smaller than the carbon black particles, the particle size of C60 is only 0.7nm, and the particles of carbon ink, active carbon and the like are all larger than 1 um. Therefore, on the premise of the same active metal content, the catalyst has better catalytic activity because the active components are more uniformly loaded; the strengthening effect of the fullerene C60 on the carrier ensures that the activity stability of the obtained catalyst is good, and the problem that the service life of the catalyst is shortened due to the adverse effect on the catalyst caused by water brought into a reaction system by long-time operation of the device or water generated in the reaction process, such as collapse of catalyst pore channels, accumulation of active metal and the like is solved. Both of the two methods can obviously improve the comprehensive economy of the hydrotreatment device, and on one hand, the preparation cost of the catalyst is effectively reduced; on the other hand, the shutdown of the industrial device and the frequent replacement of the catalyst are avoided.

In the invention, fullerene C60 with a molecular diameter of only about 7 angstroms is dissolved in toluene by adopting a method of using fullerene as a pore-expanding agent, the fullerene C60 is dissolved in toluene solution, and the fullerene is added into a catalyst carrier, so that the pore volume and the specific surface area of the alumina carrier are further increased, therefore, the particle diameter of the fullerene C60 is small, the amount of the fullerene C60 added into the alumina carrier is small and is only less than 1%, and the pore distribution of the catalyst is not diffused because of the generation of a large amount of gas in the roasting process. Only coherent pore canals with consistent pore canals and pore canals are formed, and the reaming effect with strong metal containing capacity is obtained; meanwhile, due to the excellent strength and hardness of the fullerene C60, the strength of the prepared catalyst is not damaged like other physical pore-expanding agents, and the double effects of expanding pores and increasing the strength are achieved.

In some embodiments, the fullerene in step 1) is treated by dissolving in toluene at a temperature of 20 to 40 ℃, a pressure of 0.10 to 0.25MPa and a dissolving time of 3 to 10min, wherein the mass ratio of toluene to fullerene in the toluene dissolving process is 200 to 350: 1.

in some embodiments, the step 3) comprises: adding extrusion aid in the process of mixing the slurry alumina and the fullerene solution, extruding strips for forming, and then drying and roasting.

Further, the temperature of the drying treatment is 120-160 ℃.

Further, the roasting treatment temperature is 450-700 ℃, and the roasting time is 1-15 h.

In some embodiments, the drying temperature used in the step 4) is 80 to 150 ℃, the roasting temperature is 400 to 650 ℃, and the roasting time is 1 to 15 hours.

In some embodiments, the group VIB or group VIII metal element is selected from any one or combination of two or more of molybdenum, tungsten, cobalt, and nickel, but is not limited thereto.

In some embodiments, in the catalyst of the present invention, the metal oxide includes any one or a combination of two or more of molybdenum trioxide, tungsten trioxide, nickel oxide, and cobalt oxide, but is not limited thereto.

Further, the water-soluble compound corresponding to the metal active component includes any one or a combination of two or more of ammonium molybdate, ammonium metatungstate, nickel nitrate, basic nickel carbonate, cobalt nitrate and cobalt acetate, but is not limited thereto.

In some embodiments, in the catalyst of the present invention, the alumina has a pore volume of 1.1 to 1.6cm³(ii)/g, the average pore diameter is 10 to 20 nm.

Furthermore, the amount of the fullerene is 0.1-0.6 wt%, preferably 0.2-0.5 wt% of the total mass of the carrier.

Furthermore, the fullerene is C60 fullerene powder, and the purity is more than or equal to 99.5 wt%.

Furthermore, the dosage of the nonionic surfactant is 2-8 wt% of the total mass of the carrier.

Further, the nonionic surfactant may be fatty alcohol polyether, etc., but is not limited thereto. The effect of adding the nonionic surfactant is to enable the active metal to be more fully impregnated, and the loading amount and the dispersion degree of the active metal components are improved.

The embodiment of the invention also provides a hydrogenation protection catalyst prepared by the method, and the specific surface area of the hydrogenation protection catalyst is 250-300 m²The average pore diameter is 30-50 nm, wherein the pore passage with the diameter of 10-100 nm accounts for 40-70%, and the catalyst comprises 70-96 wt% of carrier and 1-10 wt% of metal oxide.

In another aspect, the embodiment of the invention also provides the application of the hydrogenation protection catalyst in the hydrogenation treatment of inferior heavy oil.

In the method of the present invention, the low-grade heavy oil includes petroleum-based or coal-based low-grade heavy oil, such as, but not limited to, coker diesel oil, catalytic diesel oil, coker gas oil, vacuum residue, ethylene tar, catalytically cracked cycle oil, catalytically cracked oil slurry, and heavy distillate oil obtained by coal liquefaction, coal gasification or coal coking, such as coal liquefied diesel oil, wax oil and residue fraction, and anthracene oil or soft asphalt.

In conclusion, the hydrogenation protection catalyst provided by the invention has the double effects of expanding pores and increasing strength by adding fullerene as a pore-expanding agent. The particle diameter of the fullerene C60 is as small as 7 angstroms, and the addition amount is as small as less than 1 percent, so that the catalyst pore distribution is not diffused due to the generation of a large amount of gas in the roasting process. Only coherent pore canals with consistent pore canals and pore canals are formed, and the reaming effect with strong metal containing capacity is obtained; meanwhile, the fullerene C60 has excellent strength and hardness, so that the strength of the catalyst cannot be damaged like other physical pore-expanding agents; compared with the conventional hydrogenation protection catalyst, the hydrogenation protection catalyst prepared by the invention has the advantages of high strength, good activity, concentrated pore distribution, large pore volume, large specific surface area and the like, can be used for pretreating inferior heavy oil, can deeply remove heteroatoms such as Fe, Ni, V and the like and residual carbon and other macromolecular substances in the inferior raw oil, plays a role in protecting a main catalyst for subsequent hydrofining and hydrocracking, can effectively prolong the running time of the device, is suitable for treating heavy oil with high contents of metals and asphaltine, and has the characteristic of good activity stability.

The technical solution of the present invention is further explained below with reference to several embodiments and corresponding drawings.

Referring to fig. 1, the method for processing inferior heavy oil of the present invention comprises the following steps: the method comprises the steps of firstly distilling 2 inferior heavy oil 1 into light fraction 3 and heavy fraction 4, crystallizing 5 and cooling 6 the light fraction 3 to obtain a naphthalene product 7 and a naphthalene later fraction 8, extracting 9 the heavy fraction 4 by using a benzene solvent, standing 10 and separating to obtain an aromatic-rich component 11 and a colloid component 12, wherein the colloid component 12 can be used as a carbon material or a building brick raw material, distilling 14 the aromatic-rich component 11 to obtain a benzene solvent 13 and a clean aromatic-rich component 15, returning the benzene solvent 13 to be mixed with the heavy fraction 4 for recycling, mixing the clean aromatic-rich component 15 with the naphthalene later fraction 8, entering a hydrogenation reaction unit, passing through a hydrogenation refining reaction unit 16, entering a hydrogenation cracking unit 17, distilling 18 the hydrogenation cracking product to obtain products such as a gas product 19, gasoline 20, diesel oil 21 and tail oil 22, and the like, wherein surplus H in the gas product₂Separated, condensed, compressed and recycled to the hydrogenation reaction system, and mixed with new hydrogen 23 to be used as a reaction raw material and a cold medium. The tail oil 22 is mixed with the heavy fraction 4 before being recycled to the extraction step, and the reaction is restarted.

Hydrogenation protection catalyst used in the following examples of the inventionThe active metal impregnation solution is used for the preparation of the agent. The method of preparing the impregnation solution is illustrated by taking the active metals molybdenum and nickel as examples: taking a certain amount of deionized water, adding ammonium molybdate (or ammonium metatungstate) and nickel nitrate (or basic nickel carbonate, cobalt nitrate and cobalt acetate) crystals, standing after all the crystals are dissolved, and filtering to obtain metal and a dipping solution, wherein MoO₃Or WO₃The content of NiO or CoO is 2.0-10.0 g/100ml, and the content of NiO or CoO is 3.0-15.0 g/100 ml. The preparation of the active metal and the impregnation solution is well-established in the art and reference is made to the relevant literature.

The fullerene C60 used in the following examples is commercially available, and TNC60 series products of Zhongkou organic chemistry, Inc. may be used.

EXAMPLE 1 preparation of Hydroprotectant catalyst C1

(1) Preparation of catalyst carrier:

dissolving 0.50g of fullerene C60 powder with the purity of 99.5% in 138g of toluene under the pressure of 0.10MPa and at the temperature of 30 ℃ for 6min to obtain a purple fullerene solution; taking the hole with the volume of 1.1-1.6 cm³99g of commercial macroporous alumina powder per gram, and 20g of toluene are added to be beaten into slurry; adding the fullerene solution into the pasty alumina at a dropping speed of 3 g/s, fully stirring and mixing, adding an extrusion aid, such as citric acid, in the process of dropping the fullerene, wherein the amount of the extrusion aid meets the requirement of carrier forming, and then kneading, rolling and extruding into strips; airing the extruded strip-shaped carrier at room temperature, then placing the strip-shaped carrier in a drying oven to be dried for 6 hours at the temperature of 140 ℃, and breaking the strip-shaped carrier into about 3-5 mm for later use; and (4) placing the dried strip in a muffle furnace, and roasting at 580 ℃ for 8h to obtain the carrier.

(2) Preparation of the catalyst:

taking tungsten nickel solution as described above (WO)₃Content of 2.0g/100ml, NiO content of 3.0g/100ml)50ml, adding dodecyl alcohol polyether, and adding according to 5 wt% of total mass of the carrier to prepare an aqueous solution; adding 50g of the carrier prepared in the step (1) into the prepared aqueous solution for soaking, and distilling; placing the carrier impregnated with the metal in an oven, and drying for 8 hours at 120 ℃; finally, the dried product is put into a muffle furnace and roasted for 8 hours at the temperature of 550 ℃ to obtain a hydrogenation protection catalyst C1,the physical properties of the test materials are shown in Table 1.

EXAMPLE 2 preparation of Hydroprotectant catalyst C2

(1) Preparation of catalyst carrier:

dissolving 0.40g of fullerene C60 powder with the purity of 99.9% in 140g of toluene under the pressure of 0.25MPa and at the temperature of 40 ℃ for 10min to obtain a purple fullerene solution; taking the hole with the volume of 1.1-1.6 cm³99g of commercial macroporous alumina powder per gram, adding 33g of toluene and pulping; adding the fullerene solution into the pasty alumina at a dropping speed of 5 g/s, fully stirring and mixing, adding an extrusion aid, such as citric acid, in the process of dropping the fullerene, wherein the amount of the extrusion aid meets the requirement of carrier forming, and then kneading, rolling and extruding into strips; airing the extruded strip-shaped carrier at room temperature, then placing the strip-shaped carrier in a drying oven to be dried for 4 hours at 160 ℃, and breaking the strip-shaped carrier into about 3-5 mm for later use; and (3) placing the dried strip in a muffle furnace, and roasting at 450 ℃ for 15h to obtain the carrier.

(2) Preparation of the catalyst:

taking the tungsten cobalt solution as described above (WO)₃Content of 4.0g/100ml, CoO content of 6.0g/100ml)50ml, adding dodecyl alcohol polyether according to 2 wt% of total mass of the carrier to prepare aqueous solution; adding 48g of the carrier prepared in the step (1) into the prepared aqueous solution for soaking, and distilling; putting the carrier impregnated with the metal into an oven, and drying for 3 hours at 150 ℃; and finally, placing the dried product in a muffle furnace, roasting for 15h at the temperature of 400 ℃ to obtain a hydrogenation protection catalyst C2, and testing to obtain the physical properties shown in Table 1.

EXAMPLE 3 preparation of Hydroprotectant catalyst C3

(1) Preparation of catalyst carrier:

dissolving 0.30g of fullerene C60 powder with the purity of 99.5% in 60g of toluene under the pressure of 0.15MPa and at the temperature of 20 ℃ for 3min to obtain a purple fullerene solution; taking the hole with the volume of 1.1-1.6 cm³102g of commercial macroporous alumina powder per gram, adding 17g of toluene and pulping; adding the fullerene solution into the pasty alumina at a dropping speed of 2 g/s, fully stirring and mixing, adding an extrusion aid such as citric acid in the process of dropping the fullerene solution so as to meet the requirement of carrier forming, and then mixing, kneading, rolling,Extruding into strips; airing the extruded strip-shaped carrier at room temperature, then placing the strip-shaped carrier in a drying oven to be dried for 7 hours at 120 ℃, and breaking the strip-shaped carrier into about 3-5 mm for later use; and (3) placing the dried strip in a muffle furnace, and roasting at 700 ℃ for 1h to obtain the carrier.

(2) Preparation of the catalyst

Taking the molybdenum cobalt solution (MoO) as described above₃Content of 3.0g/100ml, CoO content of 5.0g/100ml)50ml, adding dodecyl alcohol polyether, and adding according to 8 wt% of total mass of the carrier to prepare aqueous solution; adding 67g of the carrier prepared in the step (1) into the prepared aqueous solution for dipping, and distilling; placing the carrier impregnated with the metal in an oven, and drying for 10 hours at 80 ℃; finally, the dried product is placed in a muffle furnace and roasted for 1h at the temperature of 650 ℃ to obtain the hydrogenation protection catalyst C3, and the physical properties of the hydrogenation protection catalyst C3 are shown in Table 1 after testing.

TABLE 1 physical Properties of C1-C3 Hydroprotection catalysts

Example 4

Fractionating the inferior heavy oil into light fraction and heavy fraction with a cut point of 225 ℃, wherein the light fraction adopts distillation and crystallization technology (the same below) well known in the art to separate crude naphthalene product and naphthalene post-fraction, and the weight yield of the crude naphthalene product is 8%; the heavy fraction was extracted with toluene under the following conditions: toluene is used as a solvent, the weight ratio of the solvent to the heavy fraction is 1:1, the extraction pressure of the solvent is normal pressure, the temperature is 60 ℃, and the weight yield of the pure aromatic-rich component is 60%. The properties of the neat aromatic rich and naphthalene afterdistillate blend oils are shown in Table 2. The properties of the gum component are shown in table 4.

This example uses a series of two reactors, the first reactor containing a hydrocrotectant C1 and a petrochemical company's commercially available hydrofinishing catalyst, e.g., 3936, the second reactor being loaded at its upper portion with a hydrofinishing catalyst, e.g., 3936, and at its lower portion with a petrochemical company's commercially available hydrocracking catalyst, e.g., 3974. In example 4, C1: 3936: 3936: 3974 the volume ratio is 23: 24: 3: 50, operating conditions and reaction results after 3000 hours of operation are shown in Table 3.

Example 5

Fractionating the inferior heavy oil into a light fraction and a heavy fraction, wherein the cutting point is 220 ℃, and the light fraction is distilled and crystallized to separate a crude naphthalene product and a naphthalene post-fraction, so that the weight yield of the crude naphthalene product is 10%; the heavy fraction is extracted by benzene under the following conditions: benzene is used as a solvent, the weight ratio of the solvent to the heavy fraction is 2:1, the extraction pressure of the solvent is normal pressure, and the temperature is 70 ℃, so that the pure aromatic-rich component weight yield is 65%. The properties of the neat aromatic rich and naphthalene afterdistillate blend oils are shown in Table 2.

The process flow, catalyst loading mode and hydrofinishing and hydrocracking catalyst types in each reactor in this example were similar to those of example 5, and the first reactor was filled with a hydrogenation-protecting catalyst C2, in this example C2: 3936: 3936: 3974 volume ratio is as follows: 23: 23: 45, operating conditions and reaction results after 3000 hours of operation are shown in Table 3.

Example 6

Fractionating the poor heavy oil into light fraction and heavy fraction, wherein the cutting point is 230 ℃, and the light fraction is distilled and crystallized to separate a crude naphthalene product and a naphthalene post-fraction, so that the weight yield of the crude naphthalene product is 9%; the heavy fraction was extracted with toluene under the following conditions: toluene is used as a solvent, the weight ratio of the solvent to the heavy fraction is 3:1, the extraction pressure of the solvent is normal pressure, and the temperature is 50 ℃, so that the pure aromatic-rich component weight yield is 63%. The properties of the neat aromatic rich and naphthalene afterdistillate blend oils are shown in Table 2.

The process flow, catalyst loading mode and hydrofinishing and hydrocracking catalyst types in each reactor in this example were similar to those of example 4, and the first reactor was filled with a hydrogenation-protecting catalyst C3, in this example C3: 3936: 3936: 3974 percent by volume as follows: 12: 20: 40, operating conditions and reaction results after 3000 hours of operation are shown in Table 3.

Comparative example 1

The hydrogenation protection catalyst of example 6 was replaced with a hydrofinishing catalyst FZC-103 commercially available from the petrochemical company, which had no fullerene addition component, and the rest of the reaction conditions and the reaction results after 3000 hours of operation as in example 5 are shown in table 3.

TABLE 2 Properties of poor heavy oil heavy fraction and naphthalene post-fraction mixed oil

Crude oil name	Example 4	Example 5	Example 6
				Distillation range/. degree.C	174/507(95v％)	168/501(95v％)	179/512(95v％)
Density (20 ℃ C.)/g-cm-3	1.07	1.05	1.08
				S/μg·g-1	386	380	405
N/μg·g-1	201	195	213

TABLE 3 hydrogenation Process conditions and product Properties

TABLE 4 Properties of the gum fraction after solvent extraction

Name (R)	Colloidal component
		H/C (atomic ratio)	0.92
Softening point/. degree.C	237
		Quinoline insoluble fraction	0.66

As shown in the above table, the high value-added products such as crude naphthalene, high-quality clean fuel oil and carbon material raw materials can be obtained by adopting the process method and the hydrogenation protection catalyst, so that the low-quality heavy oil all components are utilized, and the comprehensive economy is improved.

Through the embodiments 1 to 6, it can be found that, according to the technical scheme of the invention, the processing method of the inferior heavy oil selects a proper cutting point to fractionate the whole fraction of the inferior heavy oil, the fraction with high naphthalene content is fractionated, crude naphthalene products are obtained through rectification and crystallization, the naphthalene after-fraction and the net aromatic-rich component are mixed together to be used as the feeding material of a fixed bed hydrogenation device, and heavier colloid components are used as carbon material raw materials. On one hand, asphaltene and carbon residue which are easy to cause the inactivation of the fixed bed hydrogenation catalyst are separated out, and the high-quality feeding of the fixed bed hydrogenation device is obtained; on the other hand, the utilization rate of the inferior heavy oil is obviously improved, high value-added products such as naphthalene, clean fuel oil and the like can be obtained, and the comprehensive economy of the inferior heavy oil is improved.

In addition, the inventors have also conducted experiments with other raw materials and conditions and the like listed in the present specification by referring to the modes of examples 1 to 6, and have similarly produced a hydrogenation protection catalyst having good activity, high strength, concentrated pore distribution, large pore volume, large specific surface area and good activity stability, and also conducted effective treatment of inferior heavy oil.

It should be understood that the above-mentioned embodiments are merely illustrative of the technical concepts and features of the present invention, which are intended to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and therefore, the protection scope of the present invention is not limited thereby. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.