CN115975674A - Combined method for utilizing hydrocarbon compound - Google Patents
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Abstract
The invention relates to the field of petrochemical industry, and discloses a combined method for utilizing hydrocarbon compounds, which comprises the following steps: (1) Introducing a hydrocarbon mixture containing carbon seven and the following components into a liquid phase reactor to contact with a first catalyst, and carrying out an alkylation reaction of olefin and aromatic hydrocarbon under at least partial liquid phase conditions to generate a product A with low olefin content and low benzene content; (2) And (3) introducing the C9+ components in the product A into a gas phase reactor to contact with a second catalyst, and carrying out non-aromatic cracking, dealkylation and transalkylation reactions to generate a product B containing benzene, toluene and xylene. The method has the characteristics of low reactant consumption and optimized product structure.
Description
Technical Field
The invention relates to the field of petrochemical industry, in particular to a combination method for utilizing hydrocarbon compounds.
Background
With the application and popularization of new energy technology and the upgrading of gasoline in China, the demand of the gasoline for the automobile is gradually reduced in the future; on the other hand, with the upgrading of the quality of the gasoline, the requirements on the contents of aromatic hydrocarbon, olefin and benzene in the gasoline are further reduced. Therefore, the realization of the quality upgrading and chemical conversion of the poor gasoline is an effective way for widening the utilization of the gasoline.
The gasoline component mainly comes from a catalytic cracking and catalytic reforming unit, wherein the gasoline component in the catalytic cracking unit has higher olefin content, and the gasoline blending component in the catalytic reforming unit contains higher aromatic hydrocarbon component and is also the main source of benzene in the gasoline. At present, the quality upgrading of gasoline is realized by reducing the contents of olefin and benzene mainly through selective hydrogenation or aromatization and other reactions, chinese patent CN101767035B discloses a catalyst for producing BTX aromatic hydrocarbon by catalytic cracking gasoline and a preparation method thereof, the weight percentage of the components of the catalyst is 0.05-2.0 percent of VIII group noble metal, 0.2-5.0 percent of Zn, 0.2-5.0 percent of Sn and 5.0-80 percent of ZSM-5/ZSM-11 cocrystallized molecular sieve, the catalyst has good aromatization activity, BTX selectivity and sulfur-resistant and olefin-resistant performance, and can be used for preparing aromatic hydrocarbon by catalytic cracking gasoline or straight-run gasoline or gasoline components blended with coking, cracking and the like. Chinese patent application CN1923965A discloses a method for preparing ethylene, propylene and aromatic hydrocarbon by catalytic cracking gasoline, wherein raw materials are contacted with a catalyst once to be converted into a mixture of the ethylene, the propylene and the aromatic hydrocarbon.
In addition, alkylation of benzene with olefins is also a common method for reducing the benzene content in gasoline, for example, CN103562161B discloses a method for reducing the benzene content in gasoline by alkylating benzene with olefins, and a gasoline material is alkylated and contacted with olefins including C2-C5 olefins to produce an effluent with a low benzene content. CN103289730A discloses a method for producing high octane gasoline by alkylation of olefin-containing low carbon hydrocarbons and benzene, wherein cracking dry gas and benzene are used as raw materials, and alkylation reaction is carried out by a multistage cold shock type fixed bed reactor.
Disclosure of Invention
The invention aims to overcome the problem of high contents of olefin and benzene in the gasoline composition in the prior art, and provides a combined method for utilizing hydrocarbon compounds, which has the characteristics of low reactant consumption and optimized product structure.
In order to achieve the above object, the present invention provides a combined process for the utilization of hydrocarbon compounds, which comprises the steps of:
(1) Introducing a hydrocarbon mixture containing carbon seven and the following components into a liquid phase reactor to contact with a first catalyst, and carrying out alkylation reaction on olefin and aromatic hydrocarbon under at least partial liquid phase condition to generate a product A containing low olefin content and low benzene content;
(2) And (3) putting the C9+ components in the product A into a gas phase reactor to contact with a second catalyst, and carrying out non-aromatic cracking, dealkylation and transalkylation reactions to generate a product B containing benzene, toluene and xylene.
Preferably, the proportion of the medium-strong acid in the first catalyst is higher than 70mol% of the total acid.
Preferably, the preparation method of the first catalyst comprises:
a) Treating the molecular sieve with an alkaline medium;
b) Treating the molecular sieve obtained in the step a) by an acid medium;
c) Forming and roasting the molecular sieve obtained in the step b) and a binder to obtain a semi-finished catalyst;
d) And carrying out ammonium exchange and roasting on the catalyst semi-finished product.
Through the technical scheme, the olefin and benzene content in the gasoline can be reduced, and high-purity BTX aromatic hydrocarbon can be produced in parallel. Preferably, the first catalyst is adopted, so that the alkylation reaction degree of olefin, benzene and aromatic hydrocarbon can be better controlled, the content of olefin and benzene in the gasoline component is further reduced, and the generation of heavy components is inhibited.
Drawings
FIG. 1 is a process flow diagram of example 1 of the present invention;
FIG. 2 is a process flow diagram of example 2 of the present invention.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and these ranges or values should be understood to encompass values close to these ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
In the invention, the ratio of the medium-strong acid amount of the catalyst to the total acid amount is NH 3 -the ratio of the peak area of the TPD spectrum in the interval of 200-300 ℃ to the total peak area in the interval of 100-600 ℃.
Pore volume of the catalyst according to N 2 The adsorbate is high-purity N calculated by an adsorption and desorption method 2 The adsorption temperature is-196 ℃, the sample is subjected to vacuum pumping pretreatment for 3h at 350 ℃ before testing to remove adsorbed impurities, and the pore structure characteristic is analyzed by adopting a BJH method.
In the present invention, the specific choice of the liquid phase reactor and the gas phase reactor is not particularly limited, and may be a reactor capable of performing a reaction under liquid phase conditions or a reactor capable of performing a reaction under gas phase conditions, respectively, which are conventionally used in the art.
The invention provides a combined method for utilizing hydrocarbon compounds, which comprises the following steps:
(1) Introducing a hydrocarbon mixture containing carbon seven and the following components into a liquid phase reactor to contact with a first catalyst, and carrying out alkylation reaction on olefin and aromatic hydrocarbon under at least partial liquid phase condition to generate a product A containing low olefin content and low benzene content;
(2) And (3) putting the C9+ components in the product A into a gas phase reactor to contact with a second catalyst, and carrying out non-aromatic cracking, dealkylation and transalkylation reactions to generate a product B containing benzene, toluene and xylene.
The source of carbon seven and its components is selected from a wide range, and preferably, the carbon seven and its components are derived from aromatization products, catalytic reforming products, catalytic cracking products, steam cracking products, heavy oil hydrocracking products and any combination thereof.
According to one embodiment of the present invention, preferably, the carbon seven and its following components contain olefins and aromatics; more preferably, the olefin content is 5-40 wt% and the aromatic hydrocarbon content is 10-50 wt% based on the total amount of carbon seven and its following components.
Specifically, the carbon seven and the following components thereof may further contain an alkane, and the alkane content is preferably 20 to 60 wt%.
The expression "under at least partial liquid phase conditions" in step (1) of the present invention means that the mass fraction of the hydrocarbonaceous compound in the liquid phase in the feedstock is at least 1%.
According to the present invention, preferably, the first catalyst comprises a molecular sieve having an MWW, FAU or BEA framework structure; further preferably, the molecular sieve is selected from at least one of MCM-49, MCM-22, Y molecular sieve and Beta molecular sieve.
Preferably, the first catalyst further comprises a binder, and the content of the molecular sieve in the first catalyst is not less than 50 wt%, preferably 60-95 wt%.
The invention has wide selection range of the type of the binder, and preferably alumina and/or silica.
According to the present invention, preferably, the proportion of the medium-strong acid in the total acid amount of the first catalyst is 70mol% or more, preferably 80mol% or more, and more preferably 80 to 90mol%. The preferred embodiment is more favorable for inhibiting side reactions such as excessive alkylation and olefin polymerization at a strong acid site and reducing the generation of heavy components.
According to the invention, preferably, the first catalyst has a pore volume of 0.1cm 3 More than g, further preferably, the first catalyst has a pore volume of 0.2cm 3 A value of at least g, more preferably 0.3cm 3 A value of at least one gram, more preferably 0.3 to 0.45cm 3 /g。
As long as the first catalyst having the above structure and composition is used, it is advantageous to further optimize the product structure, and the preparation method thereof is wide in selection range, and in order to further optimize the product structure, preferably, the preparation method of the first catalyst comprises:
a) Treating the molecular sieve with an alkaline medium;
b) Treating the molecular sieve obtained in the step a) by an acid medium;
c) Forming and roasting the molecular sieve obtained in the step b) and a binder to obtain a catalyst semi-finished product;
d) And carrying out ammonium exchange and roasting on the catalyst semi-finished product.
Preferably, the alkaline medium is preferably selected from NaOH, KOH, NH 3 And an aqueous solution of an organic amine. Further preferably, the concentration of the alkaline medium is 0.05 to 2mol/L.
Preferably, the treatment temperature of the step a) is 40-100 ℃, the treatment time is 1-20 hours, and the liquid-solid mass ratio in the treatment process of the step a) is 3-10.
According to a preferred embodiment of the present invention, the process further comprises washing the molecular sieve obtained in step a) before said step b).
Preferably, the acidic medium is selected from a solution of an organic acid and/or an inorganic acid (e.g. an aqueous solution of an organic acid and/or an inorganic acid). In the present invention, the acidic medium may be a separate organic acid solution or a mineral acid solution, and may also be a solution of an organic acid and a mineral acid, preferably a solution of an organic acid and optionally a mineral acid, more preferably a solution of an organic acid and a mineral acid. When the acidic medium is a solution of an organic acid and an inorganic acid, the molar ratio of the organic acid to the inorganic acid is selected from a wide range, preferably 1: (0.1-10), for example, 1:0.5.
preferably, the organic acid is selected from one or more of citric acid, oxalic acid, acetic acid, tartaric acid.
Preferably, the inorganic acid is selected from one or more of hydrochloric acid, nitric acid, sulfuric acid.
According to a preferred embodiment of the invention, the acidic medium is selected from one or more of citric acid, oxalic acid, acetic acid, tartaric acid, hydrochloric acid, nitric acid and sulfuric acid solution. Further preferably, the concentration of the acidic medium is 0.1-5mol/L;
preferably, the treatment temperature of the step b) is 50-90 ℃, the treatment time is 1-20 hours, and the liquid-solid mass ratio in the treatment process of the step b) is 3-10.
According to a preferred embodiment of the present invention, the method further comprises washing the molecular sieve obtained in step b), drying the washed molecular sieve, and performing step c).
The shaping in step c) of the present invention is selected from a wide range, and may be, for example, a kneading type.
The firing of step c) may be performed under an air atmosphere. Preferably, the firing conditions of step c) include: the temperature is 300-600 ℃, and the time is 2-8h.
The invention has wider selection range of the ammonium exchange in the step d), and only the ammonium catalyst is obtained. The ammonium exchange may employ a water soluble ammonium salt, including but not limited to ammonium nitrate. The ammonium exchange may be carried out 1 or more times, for example 2 to 5 times. The specific conditions of the ammonium exchange are not specifically limited in the present invention, and can be performed according to conventional operations in the art, which are not described herein again.
The conditions for the calcination in step d) of the present invention are selected from a wide range, and preferably, the calcination in step d) comprises: the temperature is 300-600 ℃, and the time is 2-8h.
According to a preferred embodiment of the present invention, the reaction conditions of the liquid phase reactor include: the temperature is 100-400 ℃, the pressure is 1-7MPa, and the feeding mass space velocity is 1-8h -1 The volume ratio of hydrogen to hydrocarbon is 0-500; further preferably, the reaction conditions of the liquid phase reactor include: the temperature is 120-300 ℃, the pressure is 2-5MPa, and the feeding mass space velocity is 2-5h -1 The volume ratio of hydrogen to hydrocarbon is 0-200.
Preferably, in step (1), the olefin content in product a is reduced by more than 10%, preferably more than 20%, compared to the olefin content in the feed to the liquid phase reactor.
Preferably, in step (1), the benzene content in product a is reduced by more than 20%, preferably more than 30%, compared to the benzene content in the feed to the liquid phase reactor.
By adopting the preferred embodiment, the olefin and benzene content in the gasoline can be reduced more favorably.
It will be appreciated that, given the above disclosure, the step (1) inevitably involves other side reactions, such as olefin metathesis, in addition to the olefin/aromatic alkylation described herein.
According to a preferred embodiment of the invention, the process further comprises separating the product a to obtain C8 and less components and said C9+ components. Preferably, the method further comprises separating C8-less components from the product a as upgraded gasoline blending components.
According to a preferred embodiment of the present invention, the second catalyst is provided with at least one hydrogenation protection catalyst and at least one aromatic hydrocarbon conversion catalyst from top to bottom according to the flow direction. The hydrogenation protection catalyst and the aromatic hydrocarbon conversion catalyst can be arranged in one catalyst bed layer from top to bottom according to the material flow direction, and can also be arranged in two catalyst bed layers from top to bottom according to the material flow direction. Preferably, the hydrogenation protection catalyst and the aromatic hydrocarbon conversion catalyst are arranged in two catalyst bed layers from top to bottom according to the material flow direction.
By adopting the preferred embodiment, the hydrogenation protection catalyst is more beneficial to prolonging the service life of the aromatic hydrocarbon conversion catalyst. The role of the hydrogenation protection catalyst includes, but is not limited to, saturated olefins.
According to the present invention, preferably, the hydrogenation protection catalyst comprises a non-acidic oxide and/or a weakly acidic oxide and a metal active component. The non-acidic oxide and/or the weakly acidic oxide serve as a carrier.
Preferably, the non-acidic oxide or weakly acidic oxide is selected from Al 2 O 3 、SiO 2 At least one of MgO and CaO.
Preferably, the metal active component is selected from at least one of a group VIII non-noble metal component, a noble metal component and a group VIB metal, further preferably at least one of Pt, ni and Pd.
The invention has wide selection range of the contents of the non-acidic oxide and/or the weakly acidic oxide and the metal active component in the hydrogenation protection catalyst, and preferably, the content of the non-acidic oxide and/or the weakly acidic oxide is 80 to 99.9 weight percent based on the total amount of the hydrogenation protection catalyst, and the content of the metal active component is 0.1 to 20 weight percent calculated by oxide.
According to a preferred embodiment of the invention, the aromatic hydrocarbon conversion catalyst comprises a ten-membered ring channel silico-aluminum molecular sieve and a twelve-membered ring channel silico-aluminum molecular sieve and optionally a hydrogenation metal component. The preferred embodiment is more advantageous for obtaining high purity benzene, toluene and xylene products.
Preferably, the silicoaluminophosphate molecular sieve of the ten-membered ring channel is ZSM-5.
Preferably, the silicoaluminophosphate molecular sieves of the twelve membered ring channels are selected from at least one of MOR, beta and ZSM-12.
Preferably, the content of the silico-aluminum molecular sieve of the ten-membered ring channel is 10-90 wt%, and the content of the silico-aluminum molecular sieve of the twelve-membered ring channel is 10-90 wt%, based on the total amount of the molecular sieves in the aromatic hydrocarbon conversion catalyst.
Preferably, in the aromatics conversion catalyst, the content of the molecular sieve is 50-99 wt% and the content of the hydrogenation metal component is 0.01-10 wt% based on the total amount of the aromatics conversion catalyst. The aromatic hydrocarbon conversion catalyst also preferably contains a binder, which may be of the type described above. The content of the binder is selected from a wide range so as to satisfy the 100% principle.
Preferably, the hydrogenation metal component is selected from at least one of Mo, pt, re and Bi. More preferably, the hydrogenating metal component is Mo and Re. The content of Mo and Re is selected from a wide range, and preferably, the content of Mo is 0.5 to 5% by weight and the content of Re is 0.05 to 1% by weight, based on the total amount of the aromatic hydrocarbon conversion catalyst.
According to a preferred embodiment of the present invention, the hydrogenation protection catalyst and the aromatics conversion catalyst further comprise a step of reducing the hydrogenation protection catalyst and the aromatics conversion catalyst separately before use. The reducing conditions preferably each independently comprise: the reaction is carried out in a hydrogen atmosphere at the temperature of 300-600 ℃ for 1-5h.
The preparation methods of the hydrogenation protection catalyst and the aromatic hydrocarbon conversion catalyst are not particularly limited, and the hydrogenation protection catalyst and the aromatic hydrocarbon conversion catalyst can be prepared by adopting conventional means in the field, and the details are not repeated herein.
According to the present invention, preferably, the reaction conditions of the gas phase reactor comprise: the temperature is 300-600 ℃, the pressure is 1.5-5MPa, and the feeding mass space velocity is 1-20h -1 Hydrogen to hydrocarbon volume ratio of 100-2000; further preferably, the reaction conditions of the gas phase reactor include: the temperature is 300-450 ℃, the pressure is 2-4MPa, and the feeding mass space velocity is 2-8h -1 The volume ratio of hydrogen to hydrocarbon is 500-1000.
According to a preferred embodiment of the invention, the method further comprises: and (3) taking the benzene, the toluene and the xylene contained in the product B as products, and preferably, the purity of the benzene, the toluene and the xylene is more than 99.9%. By adopting the method provided by the invention, high-purity dimethylbenzene can be obtained.
Preferably, the process further comprises recycling the C9+ components in product B back to the gas phase reactor. This preferred embodiment makes it possible to recycle the C9+ components of the product B.
The present invention will be described in detail below by way of examples.
The following preparation examples 1 to 10 are intended to illustrate the preparation of the first catalyst of the present invention.
Preparation of example 1
Taking 20 g of Beta zeolite (the silicon-aluminum molecular ratio (Si/Al 2) is 50), adding the Beta zeolite into 100 g of NaOH solution with the concentration of 0.5mol/L, heating to 90 ℃ under stirring, keeping the temperature for 4 hours, washing with deionized water and filtering. Adding the obtained filter cake into 100 g of citric acid solution with the concentration of 0.3mol/L, heating to 90 ℃ under stirring, keeping the temperature for 4 hours, washing with deionized water, filtering and drying to obtain the acid modified molecular sieve. Kneading and molding the acid modified molecular sieve and 7.7 g of alumina, and roasting at 550 ℃ for 3 hours in air atmosphere to obtain a semi-finished catalyst; the catalyst semi-finished product is exchanged for 4 hours at 90 ℃ through an ammonium nitrate solution with the concentration of 1mol/L, filtered, and ammonium exchange is repeated for 3 times to obtain an ammonium type catalyst, and then the ammonium type catalyst is roasted for 3 hours at 500 ℃ to obtain a first catalyst, and the results are shown in Table 1.
Preparation of example 2
Taking 20 g of MCM-22 zeolite (the silicon-aluminum molecular ratio (Si/Al 2) is 30), adding the MCM-22 zeolite into 100 g of NaOH solution with the concentration of 0.3mol/L, heating to 60 ℃ under stirring, keeping the temperature for 4 hours, washing with deionized water and filtering. And adding the obtained filter cake into 100 g of citric acid solution with the concentration of 0.3mol/L, heating to 90 ℃ under stirring, keeping the temperature for 4 hours, washing with deionized water, filtering and drying to obtain the acid modified molecular sieve. Kneading and molding the acid modified molecular sieve and 7.7 g of alumina, and roasting at 550 ℃ for 3 hours in air atmosphere to obtain a semi-finished catalyst; and (3) exchanging the semi-finished catalyst product for 4 hours at 90 ℃ through an ammonium nitrate solution with the concentration of 1mol/L, filtering, repeating ammonium exchange for 3 times to obtain an ammonium catalyst, and roasting at 500 ℃ for 3 hours to obtain a first catalyst, wherein the results are shown in table 1.
Preparation of example 3
20 g of USY zeolite (the silicon-aluminum molecular ratio (Si/Al 2) is 25) is added into 100 g of NaOH solution with the concentration of 0.8mol/L, the temperature is raised to 80 ℃ under stirring and the temperature is kept constant for 4 hours, and then the USY zeolite is washed and filtered by deionized water. And adding the obtained filter cake into 100 g of citric acid solution with the concentration of 0.3mol/L, heating to 90 ℃ under stirring, keeping the temperature for 4 hours, washing with deionized water, filtering and drying to obtain the acid modified molecular sieve. Kneading and molding the acid modified molecular sieve and 7.7 g of alumina, and roasting at 550 ℃ for 3 hours in air atmosphere to obtain a semi-finished catalyst; the catalyst semi-finished product is exchanged for 4 hours at 90 ℃ through an ammonium nitrate solution with the concentration of 1mol/L, filtered, and ammonium exchange is repeated for 3 times to obtain an ammonium type catalyst, and then the ammonium type catalyst is roasted for 3 hours at 500 ℃ to obtain a first catalyst, and the results are shown in Table 1.
Preparation of example 4
The procedure of example 2 was followed except that the citric acid solution was replaced with 0.3mol/L oxalic acid solution, and the results are shown in Table 1.
Preparation of example 5
The procedure of example 2 was followed except that the citric acid solution was replaced with a mixed solution of 0.2mol/L citric acid +0.1mol/L oxalic acid solution, and the results are shown in Table 1.
Preparation of example 6
The procedure of example 2 was followed except that the citric acid solution was replaced with a mixture of 0.2mol/L citric acid +0.1mol/L hydrochloric acid solution, and the results are shown in Table 1.
Preparation of example 7
The procedure of example 2 was followed except that the citric acid solution was replaced with a mixture of 0.2mol/L citric acid +0.1mol/L sulfuric acid solution, and the results are shown in Table 1.
Preparation of example 8
Taking 20 g of MCM-22 zeolite, adding the MCM-22 zeolite into 100 g of NaOH solution with the concentration of 0.3mol/L, heating to 60 ℃ under stirring, keeping the temperature for 4 hours, washing with deionized water and filtering. Kneading the modified molecular sieve and 7.7 g of alumina for molding, and roasting at 550 ℃ for 3 hours in air atmosphere to obtain a semi-finished catalyst; and exchanging the catalyst semi-finished product for 4 hours at 90 ℃ through an ammonium nitrate solution with the concentration of 1mol/L, filtering, repeating ammonium exchange for 3 times to obtain an ammonium type catalyst, and roasting for 3 hours at 500 ℃ to obtain the first catalyst.
Preparation of example 9
Taking 20 g of MCM-22 zeolite, kneading and molding with 7.7 g of alumina, and roasting at 550 ℃ for 3 hours in air atmosphere to obtain a catalyst semi-finished product; and exchanging the catalyst semi-finished product for 4 hours at 90 ℃ through an ammonium nitrate solution with the concentration of 1mol/L, filtering, repeating ammonium exchange for 3 times to obtain an ammonium type catalyst, and roasting for 3 hours at 500 ℃ to obtain the first catalyst.
Preparation of example 10
Adding 20 g of MCM-22 zeolite into 100 g of citric acid solution with the concentration of 0.3mol/L, heating to 90 ℃ under stirring, keeping the temperature constant for 4 hours, washing with deionized water, filtering and drying to obtain the acid modified molecular sieve. Kneading the modified molecular sieve and 7.7 g of alumina for molding, and roasting at 550 ℃ for 3 hours in air atmosphere to obtain a semi-finished catalyst; and exchanging the catalyst semi-finished product for 4 hours at 90 ℃ through an ammonium nitrate solution with the concentration of 1mol/L, filtering, repeating ammonium exchange for 3 times to obtain an ammonium type catalyst, and roasting for 3 hours at 500 ℃ to obtain the first catalyst.
TABLE 1 composition of the catalyst obtained in each preparation example
Examples of Hydrocarbon mixture processing methods
The following examples are presented to illustrate the combinatorial process of the present invention, wherein:
hydrogenation protection catalyst: the catalyst is prepared by loading Pt and Ni on an alumina carrier, wherein the content of Pt is 0.1wt%, the content of Ni (calculated by metal elements) is 8wt%, and the balance is the alumina carrier, and the catalyst is reduced for 3 hours at 500 ℃ by hydrogen before being used;
aromatic hydrocarbon conversion catalyst: re-Mo modified MOR + ZSM-5 zeolite, wherein the Re content (calculated by metal elements) is 0.3wt%, the Mo content (calculated by metal elements) is 2wt%, the MOR content is 30 wt%, the ZSM-5 content is 30%, and the balance is alumina, and the catalyst is reduced by hydrogen at 400 ℃ for 3 hours before being put into use.
Example 1
The present invention will now be described more fully with reference to fig. 1. 100 tons/hour of a light component mixture of catalytic cracking dry gas, catalytic cracking gasoline and catalytic reforming gasoline (distillation range:<the raw materials are subjected to desulfurization and denitrification pretreatment at 130 ℃ (the composition condition of the obtained raw materials is shown in table 2), the raw materials enter a liquid phase alkylation unit to generate alkylation reaction between olefin and aromatic hydrocarbon, the catalyst is the first catalyst A1 prepared in preparation example 1, C8 and the following components are separated from the reaction products to be used as gasoline components, the components above C9 enter a gas phase reaction unit to generate reaction including hydrocracking and dealkylation (the operation conditions of each reaction unit are shown in table 3), and the generated products enter a separation unit to be sequentially separated to obtain C1-C5 light hydrocarbon, high-purity BTX and C9+ components. Wherein C 5 - Light hydrocarbon is extracted as a cracking raw material or a gasoline blending component, BTX is extracted as a product, and a C9+ component is circulated back to the gas phase reaction unit.
Example 2
The present invention will now be described more fully with reference to fig. 2. 100 ton/hr catalytic crackingGasoline and a light component mixture (distillation range: 40-120 ℃) of catalytic reformed gasoline are subjected to desulfurization and denitrification pretreatment (the composition condition of the obtained raw material is shown in table 2), the mixture enters a liquid phase alkylation unit to generate alkylation reaction between olefin and aromatic hydrocarbon, the catalyst is a first catalyst A1 prepared in preparation example 1, C8 and the following components are separated from reaction products to be used as gasoline components, the components above C9 enter a gas phase reaction unit to generate reaction including hydrocracking, non-aromatic cracking and dealkylation (the operating conditions of each reaction unit are shown in table 3), and the generated products enter a separation unit to be sequentially separated to obtain C1-C5 light hydrocarbon, high-purity BTX and C9+ components. Wherein C is 5 - Light hydrocarbon is extracted as a cracking raw material or a gasoline blending component, BTX is extracted as a product, and a C9+ component is recycled to the gas phase reaction unit.
Examples 3 to 11
The procedure of example 1 was followed except that the first catalysts were replaced with the first catalysts obtained in preparative examples 2 to 10, respectively, and the remaining operating conditions were unchanged, and the results are shown in Table 4.
TABLE 2 composition of the raw materials used in the examples
TABLE 3 operating conditions for examples 1-2
TABLE 4 product yield from the apparatus
The results of the examples show that the technical scheme of the invention has the effects of reducing the benzene content and the olefin content in the gasoline and inhibiting the generation of heavy components.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (10)
1. A combined process for the utilization of hydrocarbons, the process comprising the steps of:
(1) Introducing a hydrocarbon mixture containing carbon seven and the following components into a liquid phase reactor to contact with a first catalyst, and carrying out alkylation reaction on olefin and aromatic hydrocarbon under at least partial liquid phase condition to generate a product A containing low olefin content and low benzene content;
(2) And (3) putting the C9+ components in the product A into a gas phase reactor to contact with a second catalyst, and carrying out non-aromatic cracking, dealkylation and transalkylation reactions to generate a product B containing benzene, toluene and xylene.
2. The method of claim 1, wherein the carbon seven and its following components are from an aromatization product, a catalytic reforming product, a catalytic cracking product, a steam cracking product, a heavy oil hydrocracking product, and any combination thereof;
preferably, the carbon seven and its following components contain olefins and aromatics; more preferably, the olefin content is 5-40 wt% and the aromatic hydrocarbon content is 10-50 wt% based on the total amount of carbon seven and its following components.
3. The process of claim 1 or 2, wherein the first catalyst comprises a molecular sieve having a MWW, FAU or BEA framework structure;
preferably, the molecular sieve is selected from at least one of MCM-49, MCM-22, Y molecular sieve and Beta molecular sieve;
preferably, the first catalyst further comprises a binder, and the content of the molecular sieve in the first catalyst is not less than 50 wt%, preferably 60-95 wt%;
preferably, the proportion of the medium-strong acid in the first catalyst to the total acid amount is more than 70 mol%;
preferably, the first catalyst has a pore volume of 0.1cm 3 More than/g, further preferably, the pore volume of the first catalyst is 0.2cm 3 More than g.
4. The method of claim 3, wherein the first catalyst is prepared by a method comprising:
a) Treating the molecular sieve with an alkaline medium;
b) Treating the molecular sieve obtained in the step a) by an acid medium;
c) Forming and roasting the molecular sieve obtained in the step b) and a binder to obtain a semi-finished catalyst;
d) Performing ammonium exchange and roasting on the catalyst semi-finished product;
preferably, the alkaline medium is preferably selected from NaOH, KOH, NH 3 And an aqueous solution of an organic amine; further preferably, the concentration of the alkaline medium is 0.05-2mol/L;
preferably, the treatment temperature of the step a) is 40-100 ℃, the treatment time is 1-20 hours, and the liquid-solid mass ratio in the treatment process of the step a) is 3-10;
preferably, the acidic medium is selected from solutions of organic and/or inorganic acids, preferably from one or more of citric acid, oxalic acid, acetic acid, tartaric acid, hydrochloric acid, nitric acid and sulphuric acid solutions; further preferably, the concentration of the acidic medium is 0.1-5mol/L;
preferably, the treatment temperature of the step b) is 50-90 ℃, the treatment time is 1-20 hours, and the liquid-solid mass ratio in the treatment process of the step b) is 3-10.
5. The method of any of claims 1-4, wherein the reaction conditions of the liquid phase reactor comprise: the temperature is 100-400 ℃, the pressure is 1-7MPa, and the feeding mass space velocity is 1-8h -1 The volume ratio of hydrogen to hydrocarbon is 0-500;
preferably, the reaction conditions of the liquid phase reactor include: the temperature is 120-300 ℃, the pressure is 2-5MPa, and the feeding mass space velocity is 2-5h -1 Hydrogen to hydrocarbon volume ratio of 0-200;
preferably, in step (1), the olefin content in the product a is reduced by more than 10%, preferably by more than 20%, compared with the olefin content in the feed to the liquid phase reactor;
preferably, in step (1), the benzene content in product a is reduced by more than 20%, preferably more than 30%, compared to the benzene content in the feed to the liquid phase reactor.
6. The process of any one of claims 1-5 further comprising separating C8-less components from said product a as upgraded gasoline blending components.
7. The method of any of claims 1-6, wherein the second catalyst is provided with at least one hydrogenation protection catalyst and at least one aromatic conversion catalyst from top to bottom in a stream direction;
preferably, the hydrogenation protection catalyst comprises a non-acidic oxide and/or a weakly acidic oxide and a metal active component;
preferably, the non-acidic oxide or weakly acidic oxide is selected from Al 2 O 3 、SiO 2 At least one of MgO and CaO;
preferably, the metal active component is selected from at least one of a group VIII non-noble metal component, a noble metal component and a group VIB metal, further preferably at least one of Pt, ni and Pd;
preferably, the content of the non-acidic oxide and/or the weakly acidic oxide is 80 to 99.9% by weight, based on the total amount of the hydrogenation protection catalyst, and the content of the metal active component is 0.1 to 20% by weight, calculated as oxide.
8. The process of claim 7, wherein the aromatic hydrocarbon conversion catalyst contains a ten-membered ring channel silicoaluminophosphate molecular sieve and a twelve-membered ring channel silicoaluminophosphate molecular sieve and optionally a hydrogenation metal component;
preferably, the silicoaluminophosphate molecular sieve of the ten-membered ring channel is ZSM-5;
preferably, the silicoaluminophosphate molecular sieves of the twelve membered ring channels are selected from at least one of MOR, beta and ZSM-12;
preferably, the hydrogenation metal component is selected from at least one of Mo, pt, re and Bi;
preferably, in the aromatic hydrocarbon conversion catalyst, the content of the molecular sieve is 50 to 99 wt% and the content of the hydrogenation metal component is 0.01 to 10 wt% based on the total amount of the aromatic hydrocarbon conversion catalyst.
9. The method of any of claims 1-8, wherein the reaction conditions of the gas phase reactor comprise: the temperature is 300-600 ℃, the pressure is 1.5-5MPa, and the feeding mass space velocity is 1-20h -1 Hydrogen to hydrocarbon volume ratio of 100-2000;
preferably, the reaction conditions of the gas phase reactor include: the temperature is 300-450 ℃, the pressure is 2-4MPa, and the feed mass space velocity is 2-8h -1 The volume ratio of hydrogen to hydrocarbon is 500-1000.
10. The method of any one of claims 1-9, wherein the method further comprises: taking the benzene, the toluene and the xylene contained in the product B as products, preferably, the purity of the benzene, the toluene and the xylene is more than 99.9%;
preferably, the process further comprises recycling the C9+ components in product B back to the gas phase reactor.
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