CN112574781A - Processing method for treating inferior heavy oil, hydrogenation protection catalyst and application - Google Patents
Processing method for treating inferior heavy oil, hydrogenation protection catalyst and application Download PDFInfo
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- CN112574781A CN112574781A CN201910938677.2A CN201910938677A CN112574781A CN 112574781 A CN112574781 A CN 112574781A CN 201910938677 A CN201910938677 A CN 201910938677A CN 112574781 A CN112574781 A CN 112574781A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 141
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 114
- 239000000295 fuel oil Substances 0.000 title claims abstract description 79
- 238000003672 processing method Methods 0.000 title claims abstract description 15
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 claims abstract description 96
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims abstract description 86
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 claims abstract description 74
- 229910003472 fullerene Inorganic materials 0.000 claims abstract description 55
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- 238000006243 chemical reaction Methods 0.000 claims abstract description 46
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- 239000000843 powder Substances 0.000 claims abstract description 30
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- MUMZUERVLWJKNR-UHFFFAOYSA-N oxoplatinum Chemical compound [Pt]=O MUMZUERVLWJKNR-UHFFFAOYSA-N 0.000 claims description 6
- 229910003445 palladium oxide Inorganic materials 0.000 claims description 6
- 229910052697 platinum Inorganic materials 0.000 claims description 6
- 229910003446 platinum oxide Inorganic materials 0.000 claims description 6
- 239000002243 precursor Substances 0.000 claims description 6
- 229910052763 palladium Inorganic materials 0.000 claims description 5
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 4
- 239000005977 Ethylene Substances 0.000 claims description 4
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 claims description 4
- 239000010426 asphalt Substances 0.000 claims description 4
- -1 benzene compound Chemical class 0.000 claims description 4
- 238000004939 coking Methods 0.000 claims description 4
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- GTYNIXHTXBGGHQ-UHFFFAOYSA-N acetic acid osmium Chemical compound [Os].CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O GTYNIXHTXBGGHQ-UHFFFAOYSA-N 0.000 claims description 3
- CTUFHBVSYAEMLM-UHFFFAOYSA-N acetic acid;platinum Chemical compound [Pt].CC(O)=O.CC(O)=O CTUFHBVSYAEMLM-UHFFFAOYSA-N 0.000 claims description 3
- 238000005520 cutting process Methods 0.000 claims description 3
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- 229910000008 nickel(II) carbonate Inorganic materials 0.000 claims description 3
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 claims description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 3
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 3
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 claims description 3
- 239000003208 petroleum Substances 0.000 claims description 3
- NWAHZABTSDUXMJ-UHFFFAOYSA-N platinum(2+);dinitrate Chemical compound [Pt+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O NWAHZABTSDUXMJ-UHFFFAOYSA-N 0.000 claims description 3
- YEFJHNZIYIHXJQ-UHFFFAOYSA-N [Os+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O Chemical compound [Os+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YEFJHNZIYIHXJQ-UHFFFAOYSA-N 0.000 claims description 2
- 238000002309 gasification Methods 0.000 claims description 2
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- 238000004523 catalytic cracking Methods 0.000 claims 2
- 238000004090 dissolution Methods 0.000 claims 1
- 125000000373 fatty alcohol group Chemical group 0.000 claims 1
- 230000000694 effects Effects 0.000 description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 15
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- 239000002994 raw material Substances 0.000 description 10
- 239000003795 chemical substances by application Substances 0.000 description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 9
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- QPUYECUOLPXSFR-UHFFFAOYSA-N 1-methylnaphthalene Chemical compound C1=CC=C2C(C)=CC=CC2=C1 QPUYECUOLPXSFR-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
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- 244000275012 Sesbania cannabina Species 0.000 description 1
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- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
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- 150000004696 coordination complex Chemical class 0.000 description 1
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- 239000010763 heavy fuel oil Substances 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- PCLURTMBFDTLSK-UHFFFAOYSA-N nickel platinum Chemical compound [Ni].[Pt] PCLURTMBFDTLSK-UHFFFAOYSA-N 0.000 description 1
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- 229910052720 vanadium Inorganic materials 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
-
- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/464—Rhodium
-
- 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
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/892—Nickel and noble metals
-
- 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
- B01J33/00—Protection of catalysts, e.g. by coating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/66—Pore distribution
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention discloses a processing method for treating 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, the naphthalene later fraction in the light fraction and the hydrogenated tail oil, and contacting the 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 alumina powder with a boiling fullerene carbon disulfide solution at the addition rate of 4-7 g/s, extruding, forming, drying and roasting.
Description
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 for processing inferior heavy oil, which has 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 for treating 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, the naphthalene later fraction in the light fraction and the hydrogenated tail oil, 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 alumina powder with a boiling fullerene carbon disulfide solution at the adding rate of 4-7 g/s, extruding, molding, drying and roasting, the metal active component comprises a metal oxide, and the metal oxide comprises an oxide of a metal element in a VIII group; the specific surface area of the hydrogenation protection catalyst is 260-310 m2The average pore diameter is 30-50 nm, wherein the pore channels with the diameter of 10-100 nm account for 50-70%.
The embodiment of the invention also provides a preparation method of the hydrogenation protection catalyst, which comprises the following steps:
1) dissolving fullerene in carbon disulfide to obtain fullerene carbon disulfide solution, and heating to 47-55 ℃ to keep boiling;
2) adding alumina powder into the boiling fullerene carbon disulfide solution obtained in the step 1) at the adding rate of 4-7 g/s, uniformly mixing, extruding into strips, forming, and then drying and roasting to obtain a carrier;
3) 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 VIII family metal elements, and the metal active component is selected from metal oxides, then soaking the carrier obtained in the step 2) 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 50-70%, and the specific surface area is 260-310 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 for processing the inferior heavy oil divides the whole fraction of the inferior heavy oil into a light fraction and a heavy fraction, the light fraction is rectified and crystallized to obtain a crude naphthalene product and a naphthalene after-fraction, and the heavy fraction is extracted by a solvent to obtain a net aromatic-rich component and enters a hydrogenation reaction unit together with recycled hydrogenation tail oil and the naphthalene after-fraction. On one hand, asphaltene and carbon residue which are easy to cause the inactivation of the fixed bed hydrogenation catalyst are separated out, and high-quality feeding materials and carbon material raw materials of the fixed bed hydrogenation device are 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 for treating 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 treated 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 efficiency improvement of a refinery;
3) according to the invention, hydrogenation tail oil circulation, the mixture of the net aromatic-rich component and the naphthalene after-fraction are used as the feeding of the hydrogenation device, so that the conversion rate of the raw materials can be improved, the yield of gasoline and diesel oil products can be increased, and the method is also beneficial to relieving the temperature rise of the bed layer of the hydrogenation reactor;
4) the preparation method of the hydrogenation protection catalyst provided by the invention adopts fullerene as a pore-expanding agent, and has the double effects of expanding pores and increasing the strength of the catalyst. The fullerene C60 is smaller than other common physical pore-expanding agents, such as carbon black particles, the particle size of C60 is only 0.7nm, and the particles of carbon ink, activated carbon and the like are all larger than 1 um. Therefore, on the premise of the same active metal content, the catalyst provided by the invention has better catalytic activity because the active component is 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 catalyst has the advantages of good activity, high strength, reasonable pore distribution, strong metal-containing capacity and more uniform dispersion of active components, has good activity stability, is used for treating inferior heavy oil, can effectively prolong the operation period of an industrial device, reduces the operation cost of the device and improves the economy of the device;
5) the other factor of the hydrogenation protection catalyst provided by the invention that the activity and the stability are good is probably related to that fullerene C60 can form coordination compounds with metals in VIII families such as Pt, Pb, Ni, osmium and the like;
6) according to the preparation method of the hydrogenation protection catalyst, the alumina powder is added into the boiling fullerene solution at a low adding amount at a uniform speed, so that the alumina powder and the boiling fullerene solution are mixed more uniformly, and the modification effect of the fullerene on the alumina carrier is ensured;
7) 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 diagram of a process for treating heavy oil of poor quality in accordance with 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-crude 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-clean fuel oil, 21-tail oil and 22-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 processing method for treating inferior heavy oil, comprising: fractionating inferior heavy oil into light fraction and heavy fraction, separating the light fraction to obtain crude naphthalene and naphthalene later fraction, extracting the heavy fraction with 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, the naphthalene later fraction and hydrogenated tail oil together, entering 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 hydrogenated product to obtain products such as gas, gasoline, diesel oil and the like, and recycling the tail oil to mix with the aromatic-rich component and the naphthalene later fraction for restarting the hydrogenation 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 processing method for treating 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, the naphthalene later fraction in the light fraction and the hydrogenated tail oil, 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 alumina powder with a boiling fullerene carbon disulfide solution at the adding rate of 4-7 g/s, extruding, molding, drying and roasting, the metal active component comprises a metal oxide, and the metal oxide comprises an oxide of a metal element in a VIII group; the specific surface area of the hydrogenation protection catalyst is 260-310 m2The average pore diameter is 30-50 nm, wherein the pore channels with the diameter of 10-100 nm account for 50-70%.
In some embodiments, the method for processing inferior heavy oil comprises: and distilling the aromatic-rich component, removing the solvent to obtain a pure aromatic-rich component, and uniformly mixing the pure aromatic-rich component with the naphthalene after fraction and the hydrogenated tail oil 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 process for treating 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 consistent with the hydrofinishing reaction zone,namely, 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。
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 viii metal element is selected from any one or a combination of two or more of platinum, palladium, nickel, osmium, and the like, but is not limited thereto.
Accordingly, the metal oxide is selected from any one or a combination of two or more of platinum oxide, palladium oxide, nickel oxide, osmium oxide, and the like, but is not limited thereto.
Further, the metal oxide is selected from platinum oxide and/or palladium oxide, and the content of the metal oxide in the hydrogenation protection catalyst is 0.1-1.5 wt%.
Further, the metal oxide is selected from nickel oxide and/or osmium oxide, and the content of the metal oxide in the hydrogenation protection catalyst is 1.0-5.0 wt%.
In some embodiments, the method of making the carrier comprises: firstly, adding alumina powder into a fullerene carbon disulfide solution at 47-55 ℃ at a rate of 4-7 g/s for mixing, simultaneously 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 carbon disulfide solution is formed by dissolving fullerene with carbon disulfide.
In the catalyst, before the fullerene in the carrier is mixed with the alumina powder, carbon disulfide is dissolved at the dissolving temperature of 20-40 ℃, the pressure of 0.10-0.25 MPa and the dissolving time of 3-10 min; the mass ratio of carbon disulfide to fullerene adopted for dissolving carbon disulfide is 100-200: 1.
furthermore, the fullerene is C60 fullerene powder, and the purity is more than or equal to 99.5 wt%.
Further, the temperature of the drying treatment is 80-160 ℃.
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 molecule of the fullerene C60 is in a football shape, the diameter of the fullerene C60 is only 0.7nm, and the fullerene C is easily combined with an alumina carrier after being dissolved in a boiling fullerene solution, 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.
The hydrogenation protection catalyst provided by the invention adopts fullerene as a pore-expanding agent, and can form a metal complex with a metal active component to enable the active component to better play a catalytic role, 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 subsequent hydrofining and hydrocracking main catalyst, can effectively prolong the running time of a device, is suitable for treating the inferior heavy oil with high metal and asphaltene contents, and has the characteristic of good activity stability.
Another aspect of an embodiment of the present invention provides a method for preparing a hydrogenation protection catalyst, including:
1) dissolving fullerene in carbon disulfide to obtain fullerene carbon disulfide solution, and heating to 47-55 ℃ to keep boiling;
2) adding alumina powder into the boiling fullerene carbon disulfide solution obtained in the step 1) at the adding rate of 4-7 g/s, uniformly mixing, extruding into strips, forming, and then drying and roasting to obtain a carrier;
3) 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 VIII family metal elements, and the metal active component is selected from metal oxides, then soaking the carrier obtained in the step 2) into the mixed solution, and then drying and roasting to obtain the hydrogenation protection catalyst.
Another factor of the hydrogenation protection catalyst provided by the invention for good activity and stability is probably related to that fullerene C60 can form coordination compounds with metals in VIII groups such as Pt, Pb, Ni, osmium and the like.
The preparation method of the hydrogenation protection catalyst provided by the invention adopts fullerene as a pore-expanding agent, and has the double effects of expanding pores and increasing the strength of the catalyst. The fullerene C60 is smaller than other common physical pore-expanding agents, such as carbon black particles, the particle size of C60 is only 0.7nm, and the particles of carbon ink, activated carbon and the like are all larger than 1 um. Therefore, on the premise of the same active metal content, the catalyst provided by the invention has better catalytic activity because the active component is more uniformly loaded; the fullerene C60 has the advantages of good activity stability, high strength, reasonable pore distribution, high metal capacity, and more uniform dispersion of active components, and can be used for treating inferior heavy oil, effectively prolonging the operation period of industrial equipment, reducing the running cost of the equipment, and improving the economy of the equipment.
In some embodiments, the fullerene in step 1) is treated by dissolving carbon disulfide 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 carbon disulfide to fullerene in the carbon disulfide solution is 100 to 200: 1.
in some embodiments, the step 2) comprises: firstly, adding alumina powder into a fullerene carbon disulfide solution at 47-55 ℃ at a rate of 4-7 g/s for mixing, simultaneously adding an extrusion aid, extruding and forming, and then drying and roasting. According to the preparation method of the hydrogenation protection catalyst, the alumina powder is added into the boiling fullerene solution at a low adding amount at a uniform speed, so that the alumina powder and the boiling fullerene solution are mixed more uniformly, and the modification effect of the fullerene on the alumina carrier is ensured.
Further, the temperature of the drying treatment is 80-160 ℃.
Further, the roasting treatment temperature is 450-700 ℃, and the roasting time is 1-15 h.
In some embodiments, the drying temperature used in step 3) is 100 to 150 ℃, the roasting temperature is 400 to 650 ℃, and the roasting time is 1 to 15 hours.
In some embodiments, the group viii metal element is selected from any one or a combination of two or more of platinum, palladium, nickel, osmium, and the like, 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 platinum oxide, palladium oxide, nickel oxide, osmium oxide, and the like, 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 platinum nitrate, platinum acetate, palladium nitrate, palladium acetate, basic nickel carbonate, nickel nitrate, osmium acetate and the like, 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 260-310 m2The average pore diameter is 30-50 nm, wherein the pore passage with the diameter of 10-100 nm accounts for 50-70%, 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 preparation method of the hydrogenation protection catalyst provided by the invention adopts fullerene as the pore-expanding agent, and has the double effects of expanding pores and increasing the strength of the catalyst. The fullerene C60 is smaller than other common physical pore-expanding agents, such as carbon black particles, the particle size of C60 is only 0.7nm, and the particles of carbon ink, activated carbon and the like are all larger than 1 um. Therefore, on the premise of the same active metal content, the catalyst provided by the invention has better catalytic activity because the active component is more uniformly loaded; the fullerene C60 has the advantages of good activity stability, high strength, reasonable pore distribution, high metal capacity, and more uniform dispersion of active components, and can be used for treating inferior heavy oil, effectively prolonging the operation period of industrial equipment, reducing the running cost of the equipment, and improving the economy of the equipment.
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: poor heavy oil 1 is firstly distilled 2 to be divided into light fraction 3 and heavy fraction 4, the light fraction 3 is crystallized 5 and cooled 6 to obtain crude naphthalene product 7 and naphthalene later fraction 8, the heavy fraction 4 is extracted 9 by benzene solvent, and is kept still 10 to obtain aromatic-rich component 11 and colloid component 12, the colloid component 12 can be used as carbon material or building brick raw material, the aromatic-rich component 11 is distilled 14 to obtain benzene solvent 13 and pure aromatic-rich component 15, the benzene solvent 13 is returned to be mixed with the heavy fraction 4 for recycling, the pure aromatic-rich component 15 and the naphthalene later fraction 8 are mixed together and enter a hydrogenation reaction unit, and are firstly subjected to hydrogenation refining reaction unit 16The hydrorefined product is fed into hydrocracking unit 17, the hydrocracked product is distilled 18 to obtain gas product 19, clean fuel oil (gasoline and diesel oil) 20 and tail oil 21, and the excessive H in the gas product2Separated, condensed, compressed and recycled to the hydrogenation reaction system, and mixed with new hydrogen 22 to be used as a reaction raw material and a cooling medium. The tail oil 21 is mixed with the pure aromatic component 15 and the naphthalene after-fraction 8 before being recycled to the extraction process, and the hydrogenation reaction is restarted.
The following examples further illustrate the process but are not intended to be limiting.
The method of preparing the impregnation solution is illustrated by the active metals palladium and osmium: taking a certain amount of deionized water, adding palladium acetate (or palladium nitrate, platinum acetate and platinum nitrate) and osmium nitrate (or osmium acetate, basic nickel carbonate and nickel nitrate) crystals into the deionized water, standing after all the crystals are dissolved, and filtering to obtain metal and a dipping solution, wherein the content of PtO or PbO, NiO or OsO is 0.5-8.0 g/100 ml. The preparation method of the active metal and the impregnation solution is a mature technology in the field, and the relevant documents can be referred.
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:
0.40g of fullerene C60 powder with purity of 99.5% is put under pressure of 0.15MPa and at 20 deg.C with 50gCS2Dissolving for 5min to obtain fullerene solution, and heating to 47 deg.C to keep boiling state; taking 99g of commercially available macroporous alumina powder with the pore volume of 1.1-1.6 ml/g, adding the commercially available macroporous alumina powder into the fullerene boiling solution at the speed of 6 g/s, fully stirring and mixing, simultaneously adding an extrusion aid, such as citric acid, with the dosage meeting the requirement of carrier forming, and then kneading, rolling and extruding into strips; airing the extruded strip-shaped carrier at room temperature, placing the strip-shaped carrier in a drying oven, drying the strip-shaped carrier for 5 hours at the temperature of 80 ℃, and breaking the strip-shaped carrier into about 3-5 mm for later use; and (4) placing the dried strips in a muffle furnace, and roasting at 520 ℃ for 6h to obtain the carrier.
(2) Preparation of the catalyst:
taking 50ml of the palladium-osmium solution (the PdO content is 0.5g/100ml, the OsO content is 4.0g/100ml) as described above, adding the dodecyl alcohol polyether, and adding the dodecyl alcohol polyether according to 2-8 wt% of the 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; putting the carrier impregnated with the metal into an oven, and drying for 4 hours at 150 ℃; and finally, placing the dried product in a muffle furnace, and roasting for 6 hours at 520 ℃ to obtain the hydrogenation protection catalyst C1, wherein the physical properties of the hydrogenation protection catalyst C1 are shown in Table 1 after testing.
EXAMPLE 2 preparation of Hydroprotectant catalyst C2
(1) Preparation of catalyst carrier:
0.30g of fullerene C60 powder with a purity of 99.5% was put under a pressure of 0.10MPa and at 30 ℃ under 30 ℃ with a pressure of 30gCS2Dissolving for 3min to obtain fullerene solution, and heating to 51 deg.C to keep boiling state; taking 99g of commercially available macroporous alumina powder with the pore volume of 1.1-1.6 ml/g, adding the commercially available macroporous alumina powder into the fullerene boiling solution at the speed of 7 g/s, fully stirring and mixing, simultaneously adding an extrusion aid, such as citric acid, with the dosage meeting the requirement of carrier forming, and then kneading, rolling and extruding into strips; airing the extruded strip-shaped carrier at room temperature, placing the strip-shaped carrier in a drying oven, drying the strip-shaped carrier 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 50ml of palladium-nickel solution (the PdO content is 1.0g/100ml, the NiO content is 5.0g/100ml) as described above, adding dodecyl alcohol polyether, and adding the dodecyl alcohol polyether according to 2-8 wt% of the total mass of the carrier to prepare an aqueous solution; adding 49g 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 6 hours at 100 ℃; 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 C2, and the physical properties of the hydrogenation protection catalyst C2 are shown in Table 1 after testing.
EXAMPLE 3 preparation of Hydroprotectant catalyst C3
(1) Preparation of catalyst carrier:
0.50g of fullerene C60 powder with a purity of 99.9% was put under a pressure of 0.25MPa and at 40 ℃ under a pressure of 100gCS2Dissolving for 10min to obtain fullerene solution, and heating to 55 deg.C to keep it in boiling state; taking 99g of commercially available macroporous alumina powder with the pore volume of 1.1-1.6 ml/g, adding the commercially available macroporous alumina powder into the fullerene boiling solution at the speed of 4 g/s, fully stirring and mixing, simultaneously adding an extrusion aid, such as citric acid, with the dosage meeting the requirement of carrier forming, and then kneading, rolling and extruding into strips; airing the extruded strip-shaped carrier at room temperature, placing the strip-shaped carrier in a drying oven, drying the strip-shaped carrier for 6 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 50ml of the platinum-nickel solution (with PtO content of 0.8g/100ml and NiO content of 3.0g/100ml) as described above, adding dodecyl alcohol polyether according to the amount of 2-8 wt% of the total mass of the carrier, and preparing an aqueous solution; adding 60g of the carrier prepared in the step (1) into the prepared aqueous solution for dipping and distilling; putting the carrier impregnated with the metal into an oven, and drying for 4 hours at 130 ℃; and finally, placing the dried product in a muffle furnace, roasting for 15h at the temperature of 400 ℃ to obtain a hydrogenation protection catalyst C3, and testing to obtain the physical properties shown in Table 1.
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 220 ℃, 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 10%; the heavy fraction was extracted with toluene under the following conditions: benzene 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, the temperature is 60 ℃, and the weight yield of the pure aromatic-rich component is 64%. The properties of the neat aromatic rich and naphthalene afterdistillate blends 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 1, C1: 3936: 3936: 3974 the volume ratio is as follows: 20: 20: 40, operating conditions and reaction results after 3000 hours of operation are shown in Table 3.
Example 5
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%; mixing the heavy fraction and the naphthalene after-fraction, and extracting by 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, 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 blends are shown in Table 2.
The process flow, catalyst loading mode and hydrofinishing and hydrocracking catalyst types in each reactor in this example are similar to those of example 1, the first reactor is filled with a hydrogenation protection catalyst C2, in this example, C2: 3936: 3936: 3974 volume ratio is as follows: 20: 15: 50, operating conditions and reaction results after 3000 hours of operation are shown in Table 3.
Example 6
Fractionating the inferior heavy oil into light fraction and heavy fraction, wherein the cutting point is 225 ℃, 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 8%; mixing the heavy fraction and the naphthalene after-fraction, and extracting 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 50 ℃, so that the weight yield of the pure aromatic-rich component is 66%. The properties of the neat aromatic rich and naphthalene afterdistillate blends are shown in Table 2.
The process flow, catalyst loading mode and hydrofinishing and hydrocracking catalyst types in each reactor in this example are similar to those of example 1, the first reactor is filled with a hydrogenation protection catalyst C3, in this example, C3: 3936: 3936: 3974 the volume ratio is as follows: 15: 20: 45, operating conditions and reaction results after 3000 hours of operation are shown in Table 3.
Comparative example 1
The hydrocatalytic guard catalyst of example 6 was replaced with a hydrofinishing catalyst FZC-103 commercially available from the petrochemical company without the 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 clean aromatic-rich component and naphthalene afterfraction blend oil Properties
| Crude oil name | Example 4 | Example 5 | Example 6 |
| Distillation range/. degree.C | 165/501 | 169/488 | 170/491 |
| Density (20 ℃ C.)/g-cm-3 | 1.02 | 1.02 | 1.03 |
| S/μg·g-1 | 318 | 321 | 336 |
| N/μg·g-1 | 201 | 204 | 212 |
TABLE 3 hydrogenation Process conditions and product Properties
TABLE 4 Properties of the gum fraction after solvent extraction
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 processing method for processing inferior heavy oil provided by the invention, the whole fraction of the inferior heavy oil is firstly divided into light and heavy fractions, the light fraction is rectified and crystallized to obtain a crude naphthalene product and a naphthalene after-fraction, and the heavy fraction is extracted by a solvent to obtain a net aromatic-rich component, and the net aromatic-rich component and the recycled hydrogenation tail oil and the naphthalene after-fraction enter the hydrogenation reaction unit together. On one hand, asphaltene and carbon residue which are easy to cause the inactivation of the fixed bed hydrogenation catalyst are separated out, and high-quality feeding materials and carbon material raw materials of the fixed bed hydrogenation device are 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.
Claims (10)
1. A processing 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, the naphthalene later fraction in the light fraction and the hydrogenated tail oil, 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 alumina powder with a boiling fullerene carbon disulfide solution at the adding rate of 4-7 g/s, extruding, molding, drying and roasting, the metal active component comprises a metal oxide, and the metal oxide comprises an oxide of a metal element in a VIII group; the specific surface area of the hydrogenation protection catalyst is 260-310 m2The average pore diameter is 30-50 nm, wherein the pore channels with the diameter of 10-100 nm account for 50-70%.
2. The process of claim 1 wherein said process further 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 and the hydrogenated tail oil 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 process of claim 1 wherein said process further 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. a process of treating inferior heavy oil according to claim 3, wherein: 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 ratio of hydrogen to oil is 1000: 1-1400: 1, the liquid hourly space velocity is 0.3-0.7 h-1。
5. The process of claim 1 wherein said heavy oil is processed by: the hydrogenation protection catalyst comprises 70-96 wt% of a carrier and 1-10 wt% of a metal oxide;
and/or the group VIII metal element is selected from any one or combination of more than two of platinum, palladium, nickel and osmium; preferably, the metal oxide is selected from any one or a combination of two or more of platinum oxide, palladium oxide, nickel oxide and osmium oxide; particularly preferably, the metal oxide is selected from platinum oxide and/or palladium oxide, and the content of the metal oxide in the hydrogenation protection catalyst is 0.1-1.5 wt%; particularly preferably, the metal oxide is selected from nickel oxide and/or osmium oxide, and the content of the metal oxide in the hydrogenation protection catalyst is 1.0-5.0 wt%.
6. The process of claim 1, wherein the carrier is prepared by a method comprising: firstly, adding alumina powder into a fullerene carbon disulfide solution at 47-55 ℃ at a rate of 4-7 g/s for mixing, simultaneously adding an extrusion aid, extruding and 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 carbon disulfide solution is formed by dissolving fullerene with carbon disulfide; particularly preferably, the mass ratio of carbon disulfide to fullerene used for dissolving the carbon disulfide is 100-200: 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%; 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 carbon disulfide to obtain fullerene carbon disulfide solution, and heating to 47-55 ℃ to keep boiling;
2) adding alumina powder into the boiling fullerene carbon disulfide solution obtained in the step 1) at the adding rate of 4-7 g/s, uniformly mixing, extruding into strips, forming, and then drying and roasting to obtain a carrier;
3) 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 VIII family metal elements, and the metal active component is selected from metal oxides, then soaking the carrier obtained in the step 2) 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), fullerene is dissolved by carbon disulfide 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 carbon disulfide to fullerene adopted in the carbon disulfide dissolution is 100-200: 1;
and/or, the step 2) comprises: firstly, adding alumina powder into a fullerene carbon disulfide solution at 47-55 ℃ at a rate of 4-7 g/s for mixing, simultaneously adding an extrusion aid, extruding and forming, and then drying and roasting; preferably, the temperature of the drying treatment is 80-160 ℃; 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 3) is 100-150 ℃, the roasting temperature is 400-650 ℃, and the roasting time is 1-15 h;
and/or the group VIII metal element is selected from any one or combination of more than two of platinum, palladium, nickel and osmium; and/or the metal oxide is selected from any one or the combination of more than two of platinum oxide, palladium oxide, nickel oxide and osmium oxide; and/or the water-soluble compound corresponding to the metal active component comprises any one or the combination of more than two of platinum nitrate, platinum acetate, palladium nitrate, palladium acetate, basic nickel carbonate, nickel nitrate, osmium nitrate and osmium 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 50 to 70% of pore channels with diameters of 10 to 100nm are contained, and the specific surface area is 260 to 310m2And/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 petroleum-based or coal-based low-quality heavy oil, preferably coker diesel oil, catalytic diesel oil, coker wax oil, vacuum residue oil, ethylene tar, catalytic cracking cycle oil, catalytic cracking external throwing oil slurry, heavy distillate oil obtained by coal liquefaction, coal gasification or coal coking, preferably coal liquefaction diesel oil, wax oil, residue fraction, anthracene oil or soft asphalt.
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