CN115725325A - Method for reducing benzene content in gasoline and phosphorus-containing catalyst - Google Patents

Method for reducing benzene content in gasoline and phosphorus-containing catalyst Download PDF

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CN115725325A
CN115725325A CN202111014178.8A CN202111014178A CN115725325A CN 115725325 A CN115725325 A CN 115725325A CN 202111014178 A CN202111014178 A CN 202111014178A CN 115725325 A CN115725325 A CN 115725325A
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gasoline
phosphorus
content
molecular sieve
catalyst
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袁起民
马文明
毛安国
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Abstract

The present disclosure relates to a method for reducing benzene content in gasoline and a phosphorus-containing catalyst, the method comprising: introducing a gasoline raw material into a raw material separator for separation to obtain a gasoline light fraction, a gasoline middle fraction and a gasoline heavy fraction; the gasoline middle distillate and the olefin component are contacted and reacted with the catalyst in the reactor, and the reaction oil gas is led out of the reactor and then mixed with the gasoline light distillate and the gasoline heavy distillate. The present disclosure separates the gasoline feedstock into a gasoline light fraction, a gasoline middle fraction, and a gasoline heavy fraction, which may enrich benzene in the gasoline feedstock in the gasoline middle fraction. Then the fraction in the gasoline is contacted with a catalyst for reaction, so that the alkylation reaction of benzene and small molecular olefins can be promoted, and the conversion rate of benzene is improved. Benzene and micromolecular olefin are subjected to alkylation reaction in the reaction process to be converted into alkylbenzene, so that the benzene content in the gasoline can be reduced, meanwhile, the micromolecular olefin can be subjected to alkylation reaction to be converted into macromolecular olefin, and the gasoline yield is further improved.

Description

Method for reducing benzene content in gasoline and phosphorus-containing catalyst
Technical Field
The disclosure relates to the field of petrochemical industry, in particular to a method for reducing benzene content in gasoline and a phosphorus-containing catalyst.
Background
In recent years, environmental regulations and gasoline quality standards are continuously upgraded, and the olefin content, the aromatic hydrocarbon content and the benzene content in the motor gasoline are more strict than before. In gasoline pools in China, more than 70% of gasoline blending components come from catalytic cracking gasoline, and the rest of gasoline blending components include reformed gasoline, alkylate oil and the like. Benzene content in catalytically cracked gasoline and catalytically reformed gasoline also has difficulty meeting the requirements of the latest automotive gasoline standards due to the feedstock and processing technology. Therefore, the gasoline needs to be subjected to secondary treatment so as to reduce the benzene content in the oil gas.
US5491270 discloses a process for reducing the benzene content of gasoline by alkylation with larger molecular olefins. The method makes gasoline with high benzene content and olefin with larger molecule contact and react on a catalyst containing ZSM-5 molecular sieve, the method can obtain small molecule aromatic hydrocarbon and gasoline products with lower vapor pressure and sulfur content, and the benzene content of the gasoline obtained by the method is generally reduced by 25-42%.
CN1552811A discloses a method for reducing benzene content in gasoline. The method comprises mixing full-fraction catalytic cracking gasoline or light fraction of catalytic cracking gasoline with catalytic reforming gasoline according to weight ratio of 1:1-3:1, and performing alkylation reaction on ultrafine particle zeolite alkylation catalyst. Based on the weight of the catalyst, the catalyst comprises 1-10% of the sum of the contents of transition metal and lanthanide rare earth metal oxides, 50-90% of ultrafine particle zeolite, and 20-800nm of grain size of the ultrafine particle zeolite. The catalyst has strong coking resistance, good stability, low olefin and benzene content in the produced clean gasoline and small antiknock index loss.
CN101362964A discloses a catalytic conversion method for reducing the benzene content of gasoline, which comprises the steps of contacting a gasoline raw material and a gas containing micromolecule olefin with a catalytic cracking catalyst, carrying out alkylation reaction under the conditions of a temperature of 250-550 ℃, a weight hourly space velocity of 2-100h < -1 >, a reaction pressure of 0.1-1.0MPa, a weight ratio of the catalyst to the gasoline raw material of 1-30, a weight ratio of the gasoline raw material to the micromolecule olefin of 2-30 and a weight ratio of water vapor to the raw material of 0.05-1.0, feeding a reaction product into a subsequent separation system, and recycling the reacted catalyst after stripping, burning and regeneration. The method reduces the volume content of benzene in the gasoline by more than 50 percent, and improves the octane number and the yield of the gasoline.
The technology reduces the benzene content in the gasoline by means of adjusting the catalyst formula, optimizing reaction conditions and other measures, but the gasoline raw material with lower benzene content is difficult to process, and the conversion rate of benzene, the octane number of the gasoline and the yield of the gasoline are to be further improved.
Disclosure of Invention
The purpose of the present disclosure is to provide a method for reducing the benzene content in gasoline, which can be effectively applied to catalytically cracked gasoline with low benzene content, and can improve the conversion rate of benzene, the octane number of gasoline and the yield of gasoline.
In order to achieve the above object, a first aspect of the present disclosure provides a method for reducing benzene content in gasoline, the method comprising: introducing a gasoline raw material into a raw material separator for separation to obtain a gasoline light fraction, a gasoline middle fraction and a gasoline heavy fraction; and (3) enabling the gasoline middle distillate and the olefin component to contact and react with a phosphorus-containing catalyst in a reactor, and leading reaction oil gas out of the reactor to be mixed with the gasoline light distillate and the gasoline heavy distillate.
Optionally, the phosphorus-containing catalyst comprises a Y-type molecular sieve, a phosphorus-containing modified MFI structure molecular sieve, a matrix, and a binder; based on the total weight of the phosphorus-containing catalyst, the content of the Y-type molecular sieve is 10 to 70 wt%, preferably 20 to 50 wt%, the content of the phosphorus-containing modified MFI structure molecular sieve is 10 to 60 wt%, preferably 20 to 40 wt%, the content of the matrix is 10 to 70 wt%, preferably 20 to 50 wt%, and the content of the binder is 10 to 70 wt%, preferably 20 to 40 wt%.
Optionally, the Y-type molecular sieve is selected from one or more of HY, USY, REUSY, REY, REHY, DASY, and REDASY; the substrate is selected from one of amorphous silicon aluminum, aluminum oxide and silicon oxide, or a mixture of several of the amorphous silicon aluminum, the aluminum oxide and the silicon oxide; the binder is selected from one of silica sol, aluminum sol and pseudo-boehmite, or a mixture of several of the silica sol, the aluminum sol and the pseudo-boehmite.
Optionally, the phosphorus-containing modified MFI structure molecular sieve is an MFI structure molecular sieve modified with phosphorus and a metal element, the metal element comprising a rare earth metal and/or a transition metal; the MFI structure molecular sieve is selected from one or a mixture of more of ZSM-5 molecular sieve, ZSM-11 molecular sieve and ZRP molecular sieve; the transition metal is selected from one of iron, cobalt, nickel, copper, manganese, zinc and tin, or a mixture of several of the iron, cobalt, nickel, copper, manganese, zinc and tin; the rare earth metal is selected from one of lanthanum, cerium, neodymium, terbium and scandium, or a mixture of several of the lanthanum, cerium, neodymium, terbium and scandium; the content of the phosphorus is less than 5 weight percent, preferably 0.5 to 2.5 weight percent based on the total weight of the phosphorus-containing catalyst, wherein the content of the phosphorus is P 2 O 5 The content of the rare earth metal oxide is less than 10 weight percent, preferably 1 to 5 weight percent, and the content of the rare earth metal is calculated by the rare earth metal oxide; the content of the transition metal is 10% by weight or less, preferably 1 to 5% by weight.
Optionally, the transition metal is iron and/or chromium; the ratio of the total content of the transition metal and the rare earth metal oxide to the content of the phosphorus is (1.2-20): 1, preferably (2 to 5): 1.
optionally, the specific surface area of the phosphorus-containing catalyst is 110 to 130m 2 The pore volume is 0.35-0.45 ml/g, the particle diameter of D10 is 20-40 μm, the particle diameter of D50 is 60-80 μm, and the particle diameter of D90 is 105-130 μm.
Optionally, the reactor is a fluidized bed reactor, the method further comprising: introducing the gasoline middle distillate and the olefin component into the bottom of the fluidized bed reactor to contact and react with the phosphorus-containing catalyst from a catalyst riser; wherein the conditions of the contact reaction comprise: the reaction temperature is 200-500 ℃, the reaction pressure is 0.1-10 MPa, and the weight hourly space velocity of the fraction in the gasoline is 0.5-20 h -1 The weight ratio of the olefin component to the gasoline middle distillate is 1:2-40, and the fluidized bed reactorThe weight ratio of the pre-lift gas to the fraction in the gasoline is 1:2-40, and the pre-lift gas is selected from one or more of water vapor, nitrogen and dry gas.
Optionally, the temperature cut point of the gasoline light fraction and the gasoline middle fraction is 60-90 ℃, and the temperature cut point of the gasoline middle fraction and the gasoline heavy fraction is 120-150 ℃.
Optionally, the olefin component is a gas containing small molecular olefins, and the small molecular olefins are selected from olefins with 2-8 carbon atoms, preferably one or more of ethylene, propylene and butylene.
Optionally, the gasoline feedstock is catalytically cracked gasoline; the benzene content of the gasoline feedstock is 2% by volume or less, preferably 1.5% by volume or less.
Optionally, the method further comprises: separating the oil agent mixture obtained by the contact reaction to obtain a spent catalyst and the reaction oil gas; and (3) stripping the spent catalyst in a stripper, regenerating in a regenerator after stripping, and returning the obtained regenerated catalyst to the reactor for continuous use.
A second aspect of the present disclosure provides a phosphorus-containing catalyst comprising a Y-type molecular sieve, a phosphorus-containing modified MFI structure molecular sieve, a matrix, and a binder; based on the total weight of the phosphorus-containing catalyst, the content of the Y-type molecular sieve is 10 to 70 wt%, preferably 20 to 50 wt%, the content of the phosphorus-containing modified MFI structure molecular sieve is 10 to 60 wt%, preferably 20 to 40 wt%, the content of the matrix is 10 to 70 wt%, preferably 20 to 50 wt%, and the content of the binder is 10 to 70 wt%, preferably 20 to 40 wt%.
Optionally, the Y-type molecular sieve is selected from one or more of HY, USY, REUSY, REY, REHY, DASY, and REDASY; the substrate is selected from one of amorphous silicon aluminum, aluminum oxide and silicon oxide, or a mixture of several of the amorphous silicon aluminum, the aluminum oxide and the silicon oxide; the binder is selected from one of silica sol, aluminum sol and pseudo-boehmite, or a mixture of several of the silica sol, the aluminum sol and the pseudo-boehmite.
Optionally, the phosphorus-containing modified MFI structure molecular sieve is an MFI structure molecular sieve modified with phosphorus and a metal element, the metal element comprising a rare earth metal and/or a transition metal; the MFI structure molecular sieve is selected from one or a mixture of more of ZSM-5 molecular sieve, ZSM-11 molecular sieve and ZRP molecular sieve; the transition metal is selected from one of iron, cobalt, nickel, copper, manganese, zinc and tin, or a mixture of several of the iron, cobalt, nickel, copper, manganese, zinc and tin; the rare earth metal is selected from one of lanthanum, cerium, neodymium, terbium and scandium, or a mixture of several of the lanthanum, cerium, neodymium, terbium and scandium; the content of the rare earth metal is calculated by rare earth metal oxide; the content of the phosphorus is less than 5 weight percent, preferably 0.5 to 2.5 weight percent based on the total weight of the phosphorus-containing catalyst, wherein the content of the phosphorus is P 2 O 5 The content of the rare earth metal oxide is 10 wt% or less, preferably 1 to 5wt%, and the content of the transition metal is 10 wt% or less, preferably 1 to 5 wt%.
Optionally, the transition metal is iron and/or chromium; the ratio of the total content of the transition metal and the rare earth metal oxide to the content of the phosphorus is (1.2-20): 1, preferably (2 to 5): 1.
optionally, the specific surface area of the phosphorus-containing catalyst is 110 to 130m 2 The pore volume is 0.35-0.45 ml/g, the particle diameter of D10 is 20-40 μm, the particle diameter of D50 is 60-80 μm, and the particle diameter of D90 is 105-130 μm.
Through the technical scheme, the method disclosed by the invention can promote the benzene and the micromolecular olefin in the gasoline raw material to be subjected to alkylation reaction and converted into alkylbenzene, so that the conversion rate of the benzene is improved, the benzene content in the gasoline is reduced, meanwhile, the micromolecular olefin can be subjected to alkylation reaction and converted into macromolecular olefin, and the yield of the gasoline is further improved.
Additional features and advantages of the disclosure will be set forth in the detailed description which follows.
Drawings
The accompanying drawings, which are included to provide a further understanding of the disclosure and are incorporated in and constitute a part of this specification, illustrate embodiments of the disclosure and together with the description serve to explain the disclosure without limiting the disclosure. In the drawings:
FIG. 1 is a schematic diagram of a reaction apparatus used in one embodiment of the disclosed method for reducing the benzene content in gasoline.
Description of the reference numerals
1. A raw material separator; 2-1, a catalyst riser; 2-2, a stripper; 2-3, a fluidized bed reactor; 2-4, a settler; 3. a regenerator; 11. a gasoline feedstock; 12. a gasoline light fraction; 13. gasoline middle distillate; 14. a gasoline heavy fraction; 21. pre-lifting gas; 22. spent catalyst transfer lines; 23. a stripping baffle; 24. an olefin component; 25. a cyclone separator; 26. a cyclone separator; 27. a gas collection chamber; 28. reacting oil gas; 31. main wind; 32. a regenerated catalyst transfer line; 33. a cyclone separator; 34. a cyclone separator; 35. a gas collection chamber; 36. and regenerating the flue gas.
Detailed Description
The following detailed description of specific embodiments of the present disclosure is provided in connection with the accompanying drawings. It should be understood that the detailed description and specific examples, while indicating the present disclosure, are given by way of illustration and explanation only, not limitation.
In a first aspect of the present disclosure, there is provided a method for reducing the benzene content in gasoline, the method comprising: introducing a gasoline raw material into a raw material separator for separation to obtain a gasoline light fraction, a gasoline middle fraction and a gasoline heavy fraction; and (3) enabling the gasoline middle distillate and the olefin component to contact and react with a phosphorus-containing catalyst in a reactor, and leading reaction oil gas out of the reactor and mixing with the gasoline light distillate and the gasoline heavy distillate.
Through the technical scheme, the gasoline raw material is separated into the gasoline light fraction, the gasoline middle fraction and the gasoline heavy fraction, and benzene in the gasoline raw material can be enriched in the gasoline middle fraction. Then the fraction in the gasoline is contacted with the phosphorus-containing catalyst for reaction, so that the alkylation reaction of benzene and small molecular olefin can be promoted, and the conversion rate of benzene is improved. Benzene and small molecular olefin are subjected to alkylation reaction in the reaction process and converted into alkylbenzene, so that the content of benzene in gasoline can be reduced, and meanwhile, the small molecular olefin can be subjected to alkylation reaction and converted into macromolecular olefin, so that the yield of the gasoline is improved.
In one embodiment, the phosphorus-containing catalyst comprises a Y-type molecular sieve, a phosphorus-containing modified MFI structure molecular sieve, a matrix, and a binder.
In one embodiment, the Y-type molecular sieve is selected from one or more of HY, USY, REUSY, REY, REHY, DASY, and REDASY, preferably REUSY; the content of the Y-type molecular sieve is 10 to 70 weight percent, preferably 20 to 50 weight percent based on the total weight of the phosphorus-containing catalyst. Wherein the content of the Y-type molecular sieve is calculated by the weight of the charge for preparing the phosphorus-containing catalyst.
In one embodiment, the substrate is selected from one of amorphous silica-alumina, alumina and silica, or a mixture of several of them; the content of the matrix is 10 to 70 wt%, preferably 20 to 50 wt%, based on the total weight of the phosphorus-containing catalyst. Wherein the content of the matrix is calculated by the weight of the charge for preparing the phosphorus-containing catalyst.
In one embodiment, the binder is selected from one of silica sol, aluminum sol and pseudo-boehmite, or a mixture of several of them; the binder is contained in an amount of 10 to 70 wt%, preferably 20 to 40 wt%, based on the total weight of the phosphorus-containing catalyst. Wherein the content of the binder is calculated by the weight of the charge for preparing the phosphorus-containing catalyst.
In one embodiment, the phosphorus-containing modified MFI structure molecular sieve is an MFI structure molecular sieve modified with phosphorus and/or a metal element, the MFI structure molecular sieve being selected from one or more of a ZSM-5 molecular sieve, a ZSM-11 molecular sieve and a ZRP molecular sieve, preferably a ZRP molecular sieve; the content of the phosphorus-containing modified MFI structure molecular sieve is 10-60 wt%, preferably 20-40 wt%, based on the total weight of the phosphorus-containing catalyst. Wherein, the content of the phosphorus-containing modified MFI structure molecular sieve is calculated by the weight of the feed for preparing the phosphorus-containing catalyst.
In the embodiment, the phosphorus-containing catalyst uses a Y-type molecular sieve and a phosphorus-containing modified MFI structure molecular sieve, so that the alkylation reaction of benzene and small molecular olefin can be promoted, and the conversion rate of benzene can be improved. The activity of the catalyst can be enhanced by the proportion of the content of each substance in the phosphorus-containing catalyst, and when the content of each substance is in the preferable content, the activity of the catalyst can be further improved.
In one embodiment, the metal element comprises a rare earth metal and/or a transition metal; the transition metal is selected from one of iron, cobalt, nickel, copper, manganese, zinc and tin, or a mixture of several of the iron, cobalt, nickel, copper, manganese, zinc and tin, and is preferably iron and/or chromium; the rare earth metal is selected from one of lanthanum, cerium, neodymium, terbium and scandium, or a mixture of several of the lanthanum, cerium, neodymium, terbium and scandium, and preferably lanthanum.
In this embodiment, the MFI structure molecular sieve is modified with one or more of phosphorus, rare earth metals, and transition metals, which can improve the performance of the phosphorus-containing modified MFI structure molecular sieve, and further can further enhance the activity of the phosphorus-containing catalyst.
In one embodiment, the phosphorus is present in an amount of 5 wt.% or less, preferably 0.5 to 2.5 wt.%, and more preferably 0.5 to 2 wt.%, based on the total weight of the phosphorus-containing catalyst, wherein the phosphorus is present as P 2 O 5 Counting; the content of the rare earth metal oxide is 10 wt% or less, preferably 1 to 5wt%; the content of the rare earth metal is calculated by rare earth metal oxide; the content of the transition metal is 10% by weight or less, preferably 1 to 5% by weight.
In one embodiment, the transition metal is iron and/or chromium; the ratio of the total content of the transition metal and the rare earth metal oxide to the content of the phosphorus is (1.2-20): 1, preferably (2 to 5): 1. in the embodiment, the performance of the phosphorus-containing modified MFI structure molecular sieve can be further improved by the content proportion of phosphorus, rare earth metal oxide and transition metal in the phosphorus-containing catalyst, and particularly, the performance of reducing the benzene content in gasoline can be more excellent under the preferable content condition.
In one embodiment, the method further comprises preparing the phosphorus-containing catalyst by: mixing a phosphorus source, a metal source and water to obtain a mixed salt solution, carrying out impregnation treatment on an MFI structure molecular sieve raw material by using the mixed salt solution, and carrying out first drying and first roasting to obtain a phosphorus-containing modified MFI structure molecular sieve; mixing and pulping the phosphorus-containing modified MFI structure molecular sieve, the Y structure molecular sieve, the matrix, the binder and water, and then sequentially carrying out spray drying, washing, secondary drying and secondary roasting; wherein the phosphorus source is one or more selected from phosphoric acid, phosphorous acid and phosphorus pentoxide, preferably phosphorus pentoxide; the metal source is a rare earth metal source and/or a transition metal source, the rare earth metal source is selected from one of nitrate, chloride and oxide, and the transition metal source is selected from one or a mixture of nitrate, chloride and oxide; the temperature of the first drying is 100-150 ℃, and the time is 1-4 h; the temperature of the first roasting is 600-850 ℃, and the time is 2-8 h; the temperature of the second drying is 100-150 ℃, and the time is 1-6 h; the temperature of the second roasting is 650-850 ℃, and the time is 1-8 h.
In one embodiment, the reactor is a fixed bed reactor, a moving bed reactor, and a fluidized bed reactor, preferably a fluidized bed reactor; the method further comprises the following steps: introducing the gasoline middle distillate and the olefin component into the bottom of the fluidized bed reactor to contact and react with the phosphorus-containing catalyst from a catalyst riser; wherein the conditions of the contact reaction comprise: the reaction temperature is 200-500 ℃, preferably 300-450 ℃, the reaction pressure is 0.1-10 MPa, preferably 0.5-5 MPa, and the weight hourly space velocity of the fraction in the gasoline is 0.5-20 h -1 Preferably 1 to 10 hours -1 The weight ratio of the olefin component to the gasoline middle distillate is 1:2-40, preferably 1:5-30, and the weight ratio of the pre-lift gas to the gasoline middle distillate is 1:2-40, preferably 1:4-20; the pre-lift gas is selected from one or more of water vapor, nitrogen and dry gas. The processes of the present disclosure may employ reaction apparatus known in the art, including, for example, catalyst risers, strippers, fluidized bed reactors, settlers, regenerators, and cyclones.
In one embodiment, the method further comprises: the gasoline feed is preheated to 40-60 ℃ and then introduced into the separator for separation, which may be conventional in the art, and may, for example, comprise a fractionation column.
In a further embodiment, the method further comprises: preheating the olefin component to 80-150 ℃ and introducing the olefin component into the reactor.
In one embodiment, the temperature cut point of the gasoline light fraction and the gasoline medium fraction is from 60 to 90 ℃, preferably from 70 to 85 ℃; the temperature cut point of the gasoline middle fraction and the gasoline heavy fraction is 120-150 ℃, and preferably 125-145 ℃. In the embodiment, the enrichment of benzene in the fraction of gasoline can be further promoted, and further the conversion rate of benzene and the benzene reduction effect can be improved.
In one embodiment, the olefin component is a gas containing small molecule olefins selected from olefins having 2 to 8 carbon atoms, more preferably olefins having 2 to 4 carbon atoms, and preferably one or more of ethylene, propylene, and butene. In the embodiment, the micromolecular olefin has better reaction activity, can better react with benzene, and further improves the conversion rate of the benzene.
In one embodiment, the gasoline feedstock is a catalytically cracked gasoline; the benzene content of the gasoline feedstock is 2% by volume or less, preferably 1.5% by volume or less. In other embodiments of the disclosure, the processes of the present disclosure are also applicable to gasoline feedstocks having higher benzene content, such as catalytically reformed gasoline.
In this embodiment, the volume content of benzene in the gasoline after treatment of the gasoline feedstock by the process of the present disclosure may be up to 1.3 vol% or less, further up to 1.2 vol% or less, further up to 1.0 vol%.
In one embodiment, the method further comprises: separating the oil agent mixture obtained by the reaction to obtain a spent catalyst and the reaction oil gas; and (3) stripping and regenerating the spent catalyst, and returning the obtained regenerated catalyst to the reactor for continuous use.
In the embodiment, the oil agent mixture obtained by the reaction is separated to obtain the spent catalyst and the reaction oil gas; and the catalyst to be regenerated is subjected to steam stripping and regeneration, and the regenerated catalyst is introduced into the fluidized bed reactor for continuous use, so that the catalyst can be recycled, the cost is reduced, and the cost is saved.
In one embodiment, as shown in fig. 1, a method for reducing the benzene content in gasoline comprises: preheating a gasoline raw material 11 to 40-60 ℃, introducing the preheated gasoline raw material into a raw material separator 1, and separating to obtain a gasoline light fraction 12, a gasoline middle fraction 13 and a gasoline heavy fraction 14, wherein the temperature cut points of the gasoline light fraction 12 and the gasoline middle fraction 13 are 60-90 ℃, and the temperature cut points of the gasoline middle fraction 13 and the gasoline heavy fraction 14 are 120-150 ℃. Preheating the fraction 13 in the gasoline to 150-250 ℃, introducing the preheated fraction into the bottom of a fluidized bed reactor 2-3, preheating the olefin component 24 to 80-150 ℃, introducing the preheated fraction into the bottom of the fluidized bed reactor 2-3, contacting with a regenerated catalyst from a catalyst riser 2-1, and controlling the reaction temperature to 200-500 ℃, preferably 300-450 ℃, the reaction pressure to 0.1-10 MPa, preferably 0.5-5 MPa, and the weight hourly space velocity of the fraction in the gasoline to 0.5-20 h -1 Preferably 1 to 10 hours -1 The weight ratio of the olefin component to the gasoline middle distillate is 1:2-40, preferably 1:5-30, the weight ratio of the pre-lift gas to the gasoline middle distillate is 1:2-40, preferably 1:4-20, the produced oil mixture is separated by separating devices 24 and 25, the reaction oil gas is led out of the fluidized bed reactor 2-3, and the catalyst to be regenerated is led into the stripper 2-2, stripped and then led into the regenerator 3 for regeneration. The regenerated catalyst is introduced into the bottom of a catalyst riser 2-1 and enters the bottom of a fluidized bed reactor 2-3 for recycling under the lifting of pre-lift gas 21. The regeneration gas is oxygen-containing gas, including oxygen, air or a mixture of oxygen and inactive gas; the inert gas is nitrogen; the pre-lift gas 21 comprises one or more of water vapor, nitrogen gas and dry gas, and preferably water vapor.
A second aspect of the present disclosure provides an alkylation catalyst for reducing benzene content in gasoline, the phosphorus-containing catalyst comprising a Y-type molecular sieve, a phosphorus-containing modified MFI structure molecular sieve, a matrix, and a binder; based on the total weight of the phosphorus-containing catalyst, the content of the Y-type molecular sieve is 10 to 70 wt%, preferably 20 to 50 wt%, the content of the phosphorus-containing modified MFI structure molecular sieve is 10 to 60 wt%, preferably 20 to 40 wt%, the content of the matrix is 10 to 70 wt%, preferably 20 to 50 wt%, and the content of the binder is 10 to 70 wt%, preferably 20 to 40 wt%. Wherein, the contents of the Y-type molecular sieve, the matrix, the binder and the phosphorus-containing modified MFI structure molecular sieve are respectively calculated by the weight of the charge for preparing the phosphorus-containing catalyst.
In one embodiment, the Y-type molecular sieve is selected from the group consisting of HY, USY, REUSY, REY, REHY, DASY, and mixtures of one or more of reday; the substrate is selected from one of amorphous silicon aluminum, aluminum oxide and silicon oxide, or a mixture of several of the amorphous silicon aluminum, the aluminum oxide and the silicon oxide; the binder is selected from one of silica sol, aluminum sol and pseudo-boehmite, or a mixture of several of the silica sol, the aluminum sol and the pseudo-boehmite.
In one embodiment, the phosphorus-containing modified MFI structure molecular sieve is an MFI structure molecular sieve modified with phosphorus and a metal element, the metal element comprising a rare earth metal and/or a transition metal; the MFI structure molecular sieve is selected from one or a mixture of more of ZSM-5 molecular sieve, ZSM-11 molecular sieve and ZRP molecular sieve; the transition metal is selected from one of iron, cobalt, nickel, copper, manganese, zinc and tin, or a mixture of several of the iron, the nickel and the zinc are preferred; the rare earth metal is selected from one of lanthanum, cerium, neodymium, terbium and scandium, or a mixture of several of the lanthanum, cerium, neodymium, terbium and scandium, and preferably lanthanum.
In a further embodiment, the phosphorus is present in an amount of 5 wt.% or less, preferably from 0.5 to 2.5 wt.%, and more preferably from 1 to 2 wt.%, based on the total weight of the phosphorus-containing catalyst, wherein the phosphorus is present in an amount of P 2 O 5 Counting; the content of the rare earth metal oxide is 0 to 10 wt%, preferably 1 to 5wt%, and more preferably 2 to 4 wt%, and the content of the rare earth metal is calculated by the rare earth metal oxide; the content of the transition metal is 0 to 10% by weight, preferably 1 to 5% by weight, and more preferably 2 to 4% by weight. In this embodiment, the catalytic performance of the catalyst can be further improved by the selection and the preference of the content of each component substance.
In one embodiment, the transition metal is iron and/or chromium; the ratio of the total content of the transition metal and the rare earth metal oxide to the content of the phosphorus is (1.2-20): 1, preferably (2 to 5): 1.
in one embodiment, the phosphorus-containing catalyst has a specific surface area of 110 to 130m 2 A ratio of 115 to 125 m/g is preferred 2 The pore volume is 0.35 to 0.45ml/g, preferably 0.38 to 0.42ml/g, the phosphorus-containing catalyst can be in the form of particles, for example, spheroidal particles and/or spherical particles, the average particle diameter of the phosphorus-containing catalyst can be 50 to 90 μm, preferably 60 to 80 μm, the particle diameter of D10 is 20 to 40 μm, preferably 25 to 35 μm, the particle diameter of D50 is 60 to 80 μm, preferably 65 to 75 μm, and the particle diameter of D90 is 100 to 130 μm, preferably 105 to 125 μm.
The phosphorus-containing catalysts of the present disclosure can be used to treat gasoline feedstocks to reduce the benzene content of the gasoline feedstock. Preferably, the phosphorus containing catalysts of the present disclosure can be used to treat catalytically cracked gasoline; in a further embodiment, the benzene content of the gasoline feedstock is 2% by volume or less, preferably 1.5% by volume or less.
The present disclosure is further illustrated by the following examples. The starting materials used in the examples are commercially available and the reagents used below, except where specifically indicated, are chemically pure reagents.
The USY molecular sieve, the REUSY molecular sieve and the ZRP molecular sieve are all produced by a Qilu catalyst factory, and the industrial grades are as follows: and (3) USY: siO 2 2 /Al 2 O 3 ＝38。
REUSY：SiO 2 /Al 2 O 3 =41, rare earth oxide content 1.2w%;
ZRP-1：SiO 2 /Al 2 O 3 ＝50，Na 2 the content of O is 0.17wt%;
oxide: p is 2 O 5 And Re 2 O 3 ；
Metal salt: fe (NO) 3 ) 3 ·9H 2 O、Ni(NO 3 ) 2 ·6H 2 O、Cr(NO 3 ) 3 ·9H 2 O；
Kaolin: suzhou kaolin company industrial product with a solids content of 76wt%;
aluminum sol: qilu catalyst plant production of Al 2 O 3 The content was 21.5wt%;
pseudo-boehmite, produced by Shandong aluminum works.
Preparation example 1
5g P is taken 2 O 5 And 10g Fe (NO) 3 ) 3 ·9H 2 Mixing O uniformly, then adding 100g of deionized water, and uniformly stirring to obtain a mixed salt solution; taking 100g of ZRP-1 molecular sieve, slowly dripping the mixed salt solution into the ZRP-1 molecular sieve to obtain a saturated impregnation solution of the ZRP-1 molecular sieve, then carrying out first drying at 120 ℃, putting the dried solid into a roasting furnace for first roasting, and roasting at 600 ℃ for 4 hours to obtain the phosphorus-containing modified ZRP-1 molecular sieve. Taking 120g of USY molecular sieve, mixing and pulping the phosphorus-containing modified ZRP-1 molecular sieve prepared by the method and 400g of deionized water, and uniformly stirring to obtain active component slurry; uniformly mixing 100g of kaolin and 10g of alumina sol, adding 300g of deionized water, pulping, and uniformly stirring to obtain matrix slurry; adding the active component slurry into the matrix slurry, mixing and pulping, then carrying out spray drying, washing and filtering in sequence, and then carrying out secondary drying at 120 ℃ for 4 hours and secondary roasting at 700 ℃ for 6 hours to obtain the phosphorus-containing catalyst CAT-1.
Preparation example 2
Preparation of CAT-2, a phosphorus-containing catalyst, by the method of preparation 1, with the difference that the composition of the mixed salt solution is 5g P 2 O 5 、0.7g Re 2 O 3 、10g Cr(NO 3 ) 3 ·9H 2 O and 100g deionized water; the active component slurry comprises 120g of REUSY molecular sieve, phosphorus-containing modified ZRP-1 molecular sieve and 400g of deionized water.
Preparation example 3
CAT-3, a phosphorus-containing catalyst, was prepared by the process of preparation 1, with the difference that the mixed salt solution had a composition of 5g P 2 O 5 、5g Re 2 O 3 And 100g of deionized water; the active component slurry comprises 120g of USY molecular sieve, phosphorus-containing modified ZRP-1 molecular sieve and 400g of deionized water.
Preparation example 4
CAT-4, a phosphorus-containing catalyst, was prepared by the process of preparation example 1, with the difference that the mixed salt solution had a composition of 5g P 2 O 5 、12g Fe(NO 3 ) 3 ·9H 2 O、5g Re 2 O 3 And 100g of deionized water; the active component slurry comprises 120g of USY molecular sieve, phosphorus-containing modified ZRP-1 molecular sieve and 400g of deionized water.
Preparation example 5
Preparing a catalyst CAT-5 by adopting the method of preparation example 1, wherein the catalyst does not comprise a modified ZRP-1 molecular sieve, mixing 120g of USY molecular sieve and 400g of deionized water, pulping, and uniformly stirring to obtain active component slurry; uniformly mixing 100g of kaolin and 10g of alumina sol, adding 300g of deionized water, pulping, and uniformly stirring to obtain matrix slurry; adding the active component slurry into the matrix slurry, mixing and pulping, then sequentially carrying out spray drying, washing and filtering, then drying at 120 ℃ for 4 hours, and roasting at 700 ℃ for 6 hours to obtain the catalyst CAT-5.
Preparation example 6
Preparing a catalyst CAT-6 by adopting the method of preparation example 1, wherein the catalyst only comprises an unmodified ZRP-1 molecular sieve and does not comprise a USY molecular sieve, and 120g of the ZRP-1 molecular sieve and 400g of deionized water are mixed, pulped and uniformly stirred to obtain active component slurry; uniformly mixing 100g of kaolin and 10g of alumina sol, adding 300g of deionized water, pulping, and uniformly stirring to obtain matrix slurry; adding the active component slurry into the matrix slurry, mixing and pulping, then sequentially carrying out spray drying, washing and filtering, then drying for 4 hours at 120 ℃, and roasting for 6 hours at 700 ℃ to obtain the catalyst CAT-6.
Preparation example 7
CAT-7, a phosphorus-containing catalyst, was prepared by the process of preparation 1, with the difference that the mixed salt solution had a composition of 5.8g P 2 O 5 、7.5g Fe(NO 3 ) 3 ·9H 2 O and 100g of deionized water.
The compositions and properties of the catalysts obtained in preparation examples 1 to 7 are shown in Table 1.
Specific properties of the stock oils used in the examples and comparative examples are shown in Table 2. The composition of the catalytically cracked liquefied gas used is shown in table 3.
TABLE 1 composition and Properties of the catalysts
Figure BDA0003239901560000141
Figure BDA0003239901560000151
TABLE 2 composition and Properties of gasoline feedstocks
Figure BDA0003239901560000152
TABLE 3 chemical composition of catalytically cracked liquefied gas
Figure BDA0003239901560000153
Figure BDA0003239901560000161
Examples 1 to 7
The test was carried out on a test apparatus as shown in FIG. 1. Introducing a gasoline raw material into a raw material separator for separation to obtain gasoline light fraction, gasoline middle fraction and gasoline heavy fraction, introducing the gasoline middle fraction and olefin components into the bottom of a fluidized bed reactor for contact reaction with a regenerated catalyst from a catalyst riser, separating an oil agent mixture after the reaction by a separation device, performing steam stripping and regeneration on the catalyst to be regenerated for recycling, and mixing reaction oil gas led out of the reactor with the gasoline light fraction and the gasoline heavy fraction to be output as a gasoline product. The conditions under which the gasoline raw material separation, the reaction process and the regeneration process were carried out and the properties of the gasoline product are shown in Table 4.
Comparative examples 1 to 5
The test was carried out on a test apparatus as shown in FIG. 1. The conditions for carrying out the separation of the gasoline raw material, the reaction process and the regeneration process and the properties of the gasoline product are shown in Table 5.
TABLE 4 reaction conditions and results of the examples
Figure BDA0003239901560000162
Figure BDA0003239901560000171
TABLE 5 reaction conditions and reaction results of comparative examples
Figure BDA0003239901560000172
Figure BDA0003239901560000181
As can be seen from the data in tables 4 and 5, in examples 1 to 7, compared with comparative examples 1 to 5, the phosphorus-containing modified MFI structure molecular sieves provided by the method are modified and then subjected to subsequent reaction, and the method disclosed by the invention can reduce the benzene content in gasoline and improve the gasoline yield. As can be seen from a comparison of the data in examples 1 and 7, the preferred ratio of the total content of transition metal and rare earth metal oxides to the content of phosphorus in the present disclosure is (1.2-20): 1, the prepared phosphorus-containing catalyst is applied to the method of the invention, so that the benzene content in the gasoline can be more effectively reduced, and the yield of the gasoline is improved.
The preferred embodiments of the present disclosure are described in detail with reference to the accompanying drawings, however, the present disclosure is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present disclosure within the technical idea of the present disclosure, and these simple modifications all belong to the protection scope of the present disclosure.
It should be noted that the various features described in the above embodiments may be combined in any suitable manner without departing from the scope of the invention. In order to avoid unnecessary repetition, various possible combinations will not be separately described in this disclosure.
In addition, any combination of various embodiments of the present disclosure may be made, and the same should be considered as the disclosure of the present disclosure, as long as it does not depart from the spirit of the present disclosure.

Claims (16)

1. A method for reducing the benzene content of gasoline, comprising:
introducing a gasoline raw material into a raw material separator for separation to obtain a gasoline light fraction, a gasoline middle fraction and a gasoline heavy fraction;
and (3) enabling the gasoline middle distillate and the olefin component to contact and react with a phosphorus-containing catalyst in a reactor, and leading reaction oil gas out of the reactor to be mixed with the gasoline light distillate and the gasoline heavy distillate.
2. The method of claim 1, wherein the phosphorus-containing catalyst comprises a Y-type molecular sieve, a phosphorus-containing modified MFI structure molecular sieve, a matrix, and a binder; based on the total weight of the phosphorus-containing catalyst, the content of the Y-type molecular sieve is 10 to 70 wt%, preferably 20 to 50 wt%, the content of the phosphorus-containing modified MFI structure molecular sieve is 10 to 60 wt%, preferably 20 to 40 wt%, the content of the matrix is 10 to 70 wt%, preferably 20 to 50 wt%, and the content of the binder is 10 to 70 wt%, preferably 20 to 40 wt%.
3. The method of claim 2, wherein the Y-type molecular sieve is selected from the group consisting of HY, USY, REUSY, REY, REHY, DASY, and mixtures of one or more of REDASY;
the substrate is selected from one of amorphous silicon aluminum, aluminum oxide and silicon oxide, or a mixture of several of the amorphous silicon aluminum, the aluminum oxide and the silicon oxide;
the binder is selected from one of silica sol, aluminum sol and pseudo-boehmite, or a mixture of several of the silica sol, the aluminum sol and the pseudo-boehmite.
4. The process of claim 1, wherein the phosphorus-containing modified MFI structure molecular sieve is an MFI structure molecular sieve modified with phosphorus and a metal element, the metal element comprising a rare earth metal and/or a transition metal;
the MFI structure molecular sieve is selected from one or a mixture of more of ZSM-5 molecular sieve, ZSM-11 molecular sieve and ZRP molecular sieve;
the transition metal is selected from one of iron, cobalt, nickel, copper, manganese, zinc, chromium and tin, or a mixture of several of the iron, cobalt, nickel, copper, manganese, zinc, chromium and tin; the rare earth metal is selected from one of lanthanum, cerium, neodymium, terbium and scandium, or a mixture of several of the lanthanum, cerium, neodymium, terbium and scandium;
the content of the phosphorus is less than 5 weight percent, preferably 0.5 to 2.5 weight percent based on the total weight of the phosphorus-containing catalyst, wherein the content of the phosphorus is P 2 O 5 The content of the rare earth metal oxide is less than 10 weight percent, preferably 1 to 5 weight percent, and the content of the rare earth metal is calculated by the rare earth metal oxide; the content of the transition metal is 10% by weight or less, preferably 1 to 5% by weight.
5. The method according to claim 4, wherein the transition metal is iron and/or chromium; the ratio of the total content of the transition metal and the rare earth metal oxide to the content of the phosphorus is (1.2-20): 1, preferably (2 to 5): 1.
6. the process according to claim 1, wherein the phosphorus-containing catalyst has a specific surface area of 110 to 130m 2 The pore volume is 0.35-0.45 ml/g, the particle diameter of D10 is 20-40 μm, the particle diameter of D50 is 60-80 μm, and the particle diameter of D90 is 105-130 μm.
7. The method of claim 1, wherein the reactor is a fluidized bed reactor, the method further comprising: introducing the gasoline middle distillate and the olefin component into the bottom of the fluidized bed reactor to contact and react with the phosphorus-containing catalyst from a catalyst riser;
wherein the conditions of the contact reaction comprise: the reaction temperature is 200-500 ℃, the reaction pressure is 0.1-10 MPa, and the weight hourly space velocity of the fraction in the gasoline is 0.5-20 h -1 The weight ratio of the olefin component to the gasoline middle distillate is 1:2-40, the weight ratio of the pre-lifting gas of the fluidized bed reactor to the gasoline middle distillate is 1:2-40, and the pre-lifting gas is selected from one or more of steam, nitrogen and dry gas.
8. The method according to claim 1, characterized in that the temperature cut points of said gasoline light fraction and said gasoline middle fraction are between 60 and 90 ℃ and the temperature cut points of said gasoline middle fraction and said gasoline heavy fraction are between 120 and 150 ℃.
9. The method according to claim 1, wherein the olefin component is a gas containing small molecular olefins selected from olefins having 2 to 8 carbon atoms, preferably one or more of ethylene, propylene and butylene.
10. The process of claim 1, wherein the gasoline feedstock is a catalytically cracked gasoline; the benzene content of the gasoline feedstock is 2% by volume or less, preferably 1.5% by volume or less.
11. The method of claim 1, further comprising: separating the oil agent mixture obtained by the contact reaction to obtain a spent catalyst and the reaction oil gas; and (3) stripping the spent catalyst in a stripper, regenerating in a regenerator after stripping, and returning the obtained regenerated catalyst to the reactor for continuous use.
12. The phosphorus-containing catalyst is characterized by comprising a Y-type molecular sieve, a phosphorus-containing modified MFI structure molecular sieve, a matrix and a binder; based on the total weight of the phosphorus-containing catalyst, the content of the Y-type molecular sieve is 10 to 70 wt%, preferably 20 to 50 wt%, the content of the phosphorus-containing modified MFI structure molecular sieve is 10 to 60 wt%, preferably 20 to 40 wt%, the content of the matrix is 10 to 70 wt%, preferably 20 to 50 wt%, and the content of the binder is 10 to 70 wt%, preferably 20 to 40 wt%.
13. The phosphorus-containing catalyst of claim 12, wherein the Y-type molecular sieve is selected from the group consisting of HY, USY, REUSY, REY, REHY, DASY, and mixtures of one or more of REDASY;
the substrate is selected from one of amorphous silicon aluminum, aluminum oxide and silicon oxide, or a mixture of several of the amorphous silicon aluminum, the aluminum oxide and the silicon oxide;
the binder is selected from one of silica sol, aluminum sol and pseudo-boehmite, or a mixture of several of the silica sol, the aluminum sol and the pseudo-boehmite.
14. The phosphorus-containing catalyst of claim 12, wherein the phosphorus-containing modified MFI structure molecular sieve is an MFI structure molecular sieve modified with phosphorus and a metal element, the metal element comprising a rare earth metal and/or a transition metal;
the MFI structure molecular sieve is selected from one or a mixture of more of ZSM-5 molecular sieve, ZSM-11 molecular sieve and ZRP molecular sieve;
the transition metal is selected from one of iron, cobalt, nickel, copper, manganese, zinc and tin, or a mixture of several of the iron, cobalt, nickel, copper, manganese, zinc and tin; the rare earth metal is selected from one of lanthanum, cerium, neodymium, terbium and scandium, or a mixture of several of the lanthanum, cerium, neodymium, terbium and scandium;
the content of the rare earth metal is calculated by rare earth metal oxide; the content of the phosphorus is less than 5 weight percent, preferably 0.5 to 2.5 weight percent based on the total weight of the phosphorus-containing catalyst, wherein the content of the phosphorus is P 2 O 5 The rare earth metal oxide is contained in an amount of 10 wt% or less, preferably 1 to 5wt%, and the transition metal is contained in an amount of 10 wt% or less, preferablyIs selected to be 1 to 5 weight percent.
15. The method of claim 14, wherein the transition metal is iron and/or chromium; the ratio of the total content of the transition metal and the rare earth metal oxide to the content of the phosphorus is (1.2-20): 1, preferably (2 to 5): 1.
16. the phosphorus-containing catalyst according to claim 12, wherein the specific surface area of the phosphorus-containing catalyst is 110 to 130m 2 The volume of the pores is 0.35-0.45 ml/g, the particle diameter of D10 is 20-40 μm, the particle diameter of D50 is 60-80 μm, and the particle diameter of D90 is 105-130 μm.
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CN103131465A (en) * 2011-11-28 2013-06-05 上海河图工程股份有限公司 Method for reducing benzene content in gasoline
CN105505457A (en) * 2014-09-26 2016-04-20 中国石油化工股份有限公司 Method for increasing octane number of gasoline
CN112138712A (en) * 2019-06-28 2020-12-29 中国石油化工股份有限公司 Catalytic cracking catalyst, preparation method thereof and hydrocarbon oil catalytic cracking method

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5120890A (en) * 1990-12-31 1992-06-09 Uop Process for reducing benzene content in gasoline
CN101372441A (en) * 2007-08-24 2009-02-25 中国科学院大连化学物理研究所 Method for reducing benzene content in gasoline
CN102051199A (en) * 2009-10-30 2011-05-11 中国石油化工股份有限公司 Catalytic conversion method for reducing benzene content in gasoline
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