CN106631658A - Method for preparing aromatic hydrocarbon through dry gas - Google Patents
Method for preparing aromatic hydrocarbon through dry gas Download PDFInfo
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- CN106631658A CN106631658A CN201611066033.1A CN201611066033A CN106631658A CN 106631658 A CN106631658 A CN 106631658A CN 201611066033 A CN201611066033 A CN 201611066033A CN 106631658 A CN106631658 A CN 106631658A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/76—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation of hydrocarbons with partial elimination of hydrogen
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C15/00—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts
- C07C15/02—Monocyclic hydrocarbons
- C07C15/04—Benzene
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C15/00—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts
- C07C15/02—Monocyclic hydrocarbons
- C07C15/06—Toluene
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C15/00—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts
- C07C15/20—Polycyclic condensed hydrocarbons
- C07C15/24—Polycyclic condensed hydrocarbons containing two rings
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
- C07C2529/48—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The invention relates to a method for preparing aromatic hydrocarbon through dry gas. The method comprises the following steps: (1) carrying out deep and fine desulfurization; (2) carrying out oxygen removal; (3) carrying out drying; (4) conveying a purified catalysis dry gas raw material into a raw material-product heat exchanger for heat exchange, and then conveying the material into a raw material heating furnace for heating; (5) alternately feeding the catalysis dry gas into a first reactor or a second reactor for aromatization reaction to obtain a reaction product; (6) conveying the reaction product into the raw material-product heat exchanger for condensation, then conveying the reaction product into a gas-liquid separation tank to obtain a liquid phase product and a gas phase product, conveying the liquid phase product into a carbon-5 removal tower through a hybrid aromatic hydrocarbon tower, separating hydrocarbon which is smaller than carbon-5 in the liquid phase product from the tower top, separating high-purity hydrogen from the gas phase component in the gas-liquid separation tank through a pressure swing adsorption device, and conveying the residual small-molecular hydrocarbon components and the raw material together into the raw material heating furnace for recycling; (7) putting products, in which aromatic components are main components, at the bottom of the carbon-5 removal tower into a product separation and refining unit for deep separation to obtain an aromatic hydrocarbon product.
Description
Technical field
The invention belongs to the technical field of oil plant catalytic cracked dry gas comprehensive utilization of resources, and in particular to one kind is by dry
The method that gas prepares aromatic hydrocarbons.
Background technology
Currently in each factory of great oil refining, catalytic cracked dry gas are often burnt as boiler oil.Not only contain in catalysis drying gas
There is methane, the component of carbon three also containing a large amount of ethane, ethylene component and a small amount of, therefore, directly burning catalysis drying gas can cause
The huge waste of petroleum resources.
The comprehensive utilization technique of catalysis drying gas has at present catalysis drying gas ethylbenzene technology, Chinese patent (patent publication No.
CN100473715C a kind of method of utilization catalysis drying gas ethylbenzene) is disclosed, by Feedstock treating part, reactive moieties, suction
Four units of receiving portions and product separate section, the technique cross with journey corrosivity it is little, energy consumption is low, the benzene rate of recovery is high the features such as.
Chinese patent (patent publication No. CN1184136C) discloses a kind of method that utilization catalysis drying gas prepare High Purity Hydrogen, Jing
The catalysis drying gas of purified treatment and steam reaction, middle temperature transformation react and pressure-swing absorption process obtain more than 99.5% it is high-purity
Plant hydrogen.
Chinese patent (patent publication No. CN104045499B) discloses a kind of using ethylene production aromatic hydrocarbons in oil refinery dry gas
Method, the heat exchange of the oil refinery dry gas raw material Jing containing ethene enters fixed bed reactors and aromatized catalyst haptoreaction, instead
Oil gas after answering enters knockout drum carries out gas-liquid separation, and product liquid enters the isolated benzene,toluene,xylene of aromatics seperation tower
With the aromatic hydrocarbon product such as heavy aromatics.
At present, also there is not the technical scheme for clearly proposing that aromatisation is carried out using full hydrocarbon component in catalytic cracked dry gas.
In the middle of technical research, Choudhary et al. is in Low-temperature nonoxidative activation of
Methane over H-galloaluminosilicate (MFI) zeolite (Science, 1997,275 (5304)：1286-
1288) show that methane can reduce the activation temperature of methane in the presence of the auxiliary agents such as alkene, macromolecular alkane in text, make methane
Aromatization can be carried out at relatively low temperature and catalyst action, course of reaction is as follows：
CnH2n+H+→(CnH2n+1)+
CH3→CH2+H+
2CH2→C2H4
Total course of reaction is：
2CH4+2CnH2n→2CnH2n+2+C2H4。
The process had both solved the high temperature harsh conditions of methane aromatizing, it also avoid the quick carbon distribution of catalyst under high temperature,
The problem of the rapid catalyst deactivation for causing.There is substantial amounts of methane, ethene and ethane in catalysis drying gas, ethene and ethane are anti-
Answer process activation temperature relatively low, the activation of methane can be promoted, so as to by the courses of reaction such as carbochain growth, cyclisation, dehydrogenation life virtue
Hydrocarbon.
The catalysis drying gas aromatisation of indication refers to the mechanism being activated using ethene in catalysis drying gas in the present invention, compared with
Promote the activation of methane under low temperature, carbochain occurs jointly by ethene, ethane and methane in catalysis drying gas and increases, be cyclized, take off
The courses of reaction such as hydrogen generate aromatic hydrocarbon product, and this process is with the cracking of some hydrocarbon, the process of condensation coking.
The content of the invention
Goal of the invention：The present invention makes improvement for the problem that above-mentioned prior art is present, i.e., the invention discloses a kind of
The method that aromatic hydrocarbons is prepared by dry gas.
Technical scheme：A kind of method for preparing aromatic hydrocarbons by dry gas, comprises the following steps：
(1) depth fine de-sulfur
(11) first grade desulfurizing
Catalysis drying gas are sent into into normal temperature iron oxide fine de-hydrogen sulfide column, hydrogen sulfide in dry gas is taken off to below 1ml/L, its
In：Normal temperature iron oxide fine de-hydrogen sulfide column operating condition is：
20～40 DEG C of operating temperature,
500～1500h of volume space velocity-1；
(12) two-grade desulfurizing
The de- small molecule mercaptan tower of normal temperature NaX molecular sieves will be sent into through the catalysis drying gas of first grade desulfurizing, by catalysis drying gas
Mercaptan is taken off to below 1ml/L, and the operating condition of the de- small molecule mercaptan tower of normal temperature NaX molecular sieves is：
20～40 DEG C of operating temperature,
500～1500h of volume space velocity-1；
(2) deoxygenation
By the catalysis drying gas after secondary desulfuration by loading CuO-MnO2Remove in the deoxidation tower of bimetallic deoxidier
Oxygen, oxygen content in catalysis drying gas is removed to less than 10ml/L, CuO and MnO2Active component weight content be 70～
90%, remaining is aluminum oxide, CuO and MnO2Ratio be (1～3)：10, load CuO-MnO2The deoxidation tower of bimetallic deoxidier
Operating condition be：
2000～3000h of volume space velocity-1,
Operating temperature is normal temperature；
(3) it is dried
To be adsorbed by drying by loading the dehydrating tower of 3A molecular sieves through the catalysis drying gas of deoxygenation, drying condition is：
1000～2000h of volume space velocity-1, water content in dry gas is down to below 1ml/l by normal temperature；
(4) raw material-product exchanger heat exchange will be first sent into through dry purifying and catalyzing dry gas raw material, is then re-fed into original
Material heating furnace is heated to 400～550 DEG C；
(5) by step (4), through the catalysis drying gas of heating, alternately being passed through first reactor or second reactor carries out aromatization
Change reaction and obtain product, wherein：
Catalysis drying gas aromatized catalyst has been loaded in first reactor and second reactor；
(6) product that step (5) is obtained first is sent in raw material-product exchanger and is condensed, it is cooled to 30～
After 60 DEG C, then it is sent to knockout drum and obtains liquid product and gas-phase product, liquid product is pumped into through BTX aromatics
The tower of decarburization five, the hydro carbons in liquid product less than carbon five is separated from tower top, and is become with the gaseous component Jing in knockout drum
Pressure adsorbent equipment isolates high-purity hydrogen, and remaining small molecule hydrocarbon component together mixes feeding raw materials furnace and heating with raw material and returns
Refining；
(7) bottom of the tower of decarburization five is mainly aromatic component, carries out depth into product separation and purification unit isolated
Aromatic hydrocarbon product.
Further, step (5) the catalysis drying gas aromatized catalyst is the Mo/ZSM-5 catalyst of additive modification, its
In：
The weight content of ZSM-5 molecular sieve is 20～90wt%,
The weight content of metal Mo oxides is 0.1～10wt%,
The weight content of modified additive is 0.1～10wt%,
Remaining is aluminum oxide.
Further, step (5) the catalysis drying gas aromatized catalyst is the Mo/ZSM-5 catalyst of additive modification,
Wherein：
The weight content of ZSM-5 molecular sieve is 50～70wt%,
The weight content of metal Mo oxides is 5～8wt%,
The weight content of modified additive is 0.5～3wt%,
Remaining is aluminum oxide.
Further, one or more during the modified additive of catalyst is for B, P, F, Cl, Zr, Cr, Zn, La and Ce.
Further, in step (5) first reactor and second reactor is in parallel, using reactor switching behaviour in operation
Make, a reactor normal reaction production, another reactor carries out catalyst regenerative operation.
Further, the reaction condition of first reactor and second reactor is：
Reaction pressure is 0.1～1.0MPa,
Reaction temperature is 500～650 DEG C,
Reaction volume air speed is 500～2000h-1,
Catalyst one way service cycle is in 200～400h.
Further, the catalyst after inactivating in first reactor and second reactor is carried out using oxygen containing inert gas
Regeneration, wherein
Oxygen content is 0.5～5.0vol%,
Regeneration temperature is 400～500 DEG C,
Pressure is 0.1～3.0MPa,
Gas/agent volume ratio is 250～1000.
Further, inert gas is nitrogen.
Beneficial effect：A kind of method for preparing aromatic hydrocarbons by dry gas disclosed by the invention has the advantages that：
(1) compared with the oxygen-free aromatization reaction of natural gas, can effectively reduce because there is substantial amounts of ethene in catalysis drying gas
The activation temperature of methane, reduces methane conversion temperature, reduces catalyst carbon deposition, improves catalyst life and stability；
(2) contain C3～C 5 fraction in circulating air, the conversion of methane can be promoted.
(3) the main benzene of product, toluene and naphthalene, methane conversion is high, and arenes selectivity is high.
Description of the drawings
Fig. 1 is a kind of schematic flow sheet of method that aromatic hydrocarbons is prepared by dry gas disclosed by the invention,
Wherein：
1- purifying and catalyzing dry gas raw material 2- raw materials-product exchanger
3- raw materials furnace and heating 4- first reactors
5- second reactor 6- knockout drums
The tower of 7- BTX aromatics pump 8- decarburizations five
9- pressure-swing absorption apparatus 10- aromatic hydrocarbon products
11- high-purity hydrogens
Specific embodiment：
The specific embodiment of the present invention is described in detail below.
Specific embodiment 1
As shown in figure 1, a kind of method for preparing aromatic hydrocarbons by dry gas, comprises the following steps：
(1) depth fine de-sulfur
(11) first grade desulfurizing
Catalysis drying gas are sent into into normal temperature iron oxide fine de-hydrogen sulfide column, hydrogen sulfide in dry gas is taken off to below 1ml/L, its
In：Normal temperature iron oxide fine de-hydrogen sulfide column operating condition is：
20 DEG C of operating temperature,
Volume space velocity 500h-1；
(12) two-grade desulfurizing
The de- small molecule mercaptan tower of normal temperature NaX molecular sieves will be sent into through the catalysis drying gas of first grade desulfurizing, by catalysis drying gas
Mercaptan is taken off to below 1ml/L, and the operating condition of the de- small molecule mercaptan tower of normal temperature NaX molecular sieves is：
20 DEG C of operating temperature,
Volume space velocity 500h-1；
(2) deoxygenation
By the catalysis drying gas after secondary desulfuration by loading CuO-MnO2Remove in the deoxidation tower of bimetallic deoxidier
Oxygen, oxygen content in catalysis drying gas is removed to less than 10ml/L, CuO and MnO2Active component weight content is 70%, its
It is remaining for aluminum oxide, CuO and MnO2Ratio be 1：10, load CuO-MnO2The operating condition of the deoxidation tower of bimetallic deoxidier is：
Volume space velocity 2000h-1,
Operating temperature is normal temperature；
(3) it is dried
To be adsorbed by drying by loading the dehydrating tower of 3A molecular sieves through the catalysis drying gas of deoxygenation, drying condition is：
Volume space velocity 1000h-1, water content in dry gas is down to below 1ml/l by normal temperature；
(4) will first send into raw material-product exchanger 2 through dry purifying and catalyzing dry gas raw material 1 to exchange heat, be then re-fed into
Raw materials furnace and heating 3 is heated to 400 DEG C；
(5) by step (4), through the catalysis drying gas of heating, alternately being passed through first reactor 4 or second reactor 5 carries out virtue
Structureization reaction obtains product, wherein：
Catalysis drying gas aromatized catalyst has been loaded in first reactor 4 and second reactor 5；
(6) product that step (5) is obtained first is sent in raw material-product exchanger 2 and is condensed, be cooled to 30 DEG C
Afterwards, then it is sent to knockout drum 6 and obtains liquid product and gas-phase product, liquid product is sent into de- through BTX aromatics pump 7
The tower 8 of carbon five, the hydro carbons in liquid product less than carbon five is separated from tower top, and is become with the gaseous component Jing in knockout drum 6
Pressure adsorbent equipment 9 isolates high-purity hydrogen 11, and remaining small molecule hydrocarbon component together mixes feeding raw materials furnace and heating 3 with raw material
Freshening；
(7) bottom of the tower 8 of decarburization five is mainly aromatic component, carries out depth into product separation and purification unit isolated
Aromatic hydrocarbon product 10.
Further, step (5) the catalysis drying gas aromatized catalyst is the Mo/ZSM-5 catalyst of additive modification, its
In：
The weight content of ZSM-5 molecular sieve is 20wt%,
The weight content of metal Mo oxides is 0.1wt%,
The weight content of modified additive is 0.1wt%,
Further, the modified additive of catalyst is B.
Further, the first reactor 4 and second reactor 5 in step (5) is in parallel, is switched using reactor in operation
Operation, a reactor normal reaction production, another reactor carries out catalyst regenerative operation.
Further, the reaction condition of first reactor 4 and second reactor 5 is：
Reaction pressure is 0.1MPa,
Reaction temperature is 550 DEG C,
Reaction volume air speed is 1500h-1,
Catalyst one way service cycle is in 200h.
Further, the catalyst after inactivating in first reactor 4 and second reactor 5 is entered using oxygen containing inert gas
Row regeneration, wherein
Oxygen content is 0.5vol%,
Regeneration temperature is 400 DEG C,
Pressure is 0.1MPa,
Gas/agent volume ratio is 250.
Further, inert gas is nitrogen.
Present invention process raw material is designed as Jing desulfurization, deoxidation, dried catalysis drying gas, the catalysis that the present embodiment is used
Dry gas composition is shown in Table 1.
Table 2 is conversion ratio and choosing of the catalysis drying gas respectively through fresh catalyst and regenerated catalyst in the differential responses time
Selecting property.Catalysis drying gas are shown by fixed bed reactors by the evaluation result of table 2, for fresh catalyst and urging through regeneration
Agent, catalysis drying gas conversion ratio can reach more than 30% during stable reaction, and wherein methane converts reachable more than 15%, aromatic hydrocarbons
Selectively reach near 99%, with excellent catalytic perfomance.
The unstripped gas of table 1 is constituted
Catalysis drying gas aromatization performance (550 DEG C of reaction temperature, the volume space velocity 1500h of the differential responses time of table 2-1)
Specific embodiment 2
As shown in figure 1, a kind of method for preparing aromatic hydrocarbons by dry gas, comprises the following steps：
(1) depth fine de-sulfur
(11) first grade desulfurizing
Catalysis drying gas are sent into into normal temperature iron oxide fine de-hydrogen sulfide column, hydrogen sulfide in dry gas is taken off to below 1ml/L, its
In：Normal temperature iron oxide fine de-hydrogen sulfide column operating condition is：
40 DEG C of operating temperature,
Volume space velocity 1500h-1；
(12) two-grade desulfurizing
The de- small molecule mercaptan tower of normal temperature NaX molecular sieves will be sent into through the catalysis drying gas of first grade desulfurizing, by catalysis drying gas
Mercaptan is taken off to below 1ml/L, and the operating condition of the de- small molecule mercaptan tower of normal temperature NaX molecular sieves is：
40 DEG C of operating temperature,
Volume space velocity 1500h-1；
(2) deoxygenation
By the catalysis drying gas after secondary desulfuration by loading CuO-MnO2Remove in the deoxidation tower of bimetallic deoxidier
Oxygen, oxygen content in catalysis drying gas is removed to less than 10ml/L, CuO and MnO2Active component weight content be 70～
90%, remaining is aluminum oxide, CuO and MnO2Ratio be 3：10, load CuO-MnO2The operation of the deoxidation tower of bimetallic deoxidier
Condition is：
Volume space velocity 3000h-1,
Operating temperature is normal temperature；
(3) it is dried
To be adsorbed by drying by loading the dehydrating tower of 3A molecular sieves through the catalysis drying gas of deoxygenation, drying condition is：
Volume space velocity 2000h-1, water content in dry gas is down to below 1ml/l by normal temperature；
(4) will first send into raw material-product exchanger 2 through dry purifying and catalyzing dry gas raw material 1 to exchange heat, be then re-fed into
Raw materials furnace and heating 3 is heated to 550 DEG C；
(5) by step (4), through the catalysis drying gas of heating, alternately being passed through first reactor 4 or second reactor 5 carries out virtue
Structureization reaction obtains product, wherein：
Catalysis drying gas aromatized catalyst has been loaded in first reactor 4 and second reactor 5；
(6) product that step (5) is obtained first is sent in raw material-product exchanger 2 and is condensed, be cooled to 60 DEG C
Afterwards, then it is sent to knockout drum 6 and obtains liquid product and gas-phase product, liquid product is sent into de- through BTX aromatics pump 7
The tower 8 of carbon five, the hydro carbons in liquid product less than carbon five is separated from tower top, and is become with the gaseous component Jing in knockout drum 6
Pressure adsorbent equipment 9 isolates high-purity hydrogen 11, and remaining small molecule hydrocarbon component together mixes feeding raw materials furnace and heating 3 with raw material
Freshening；
(7) the bottom position of the tower 8 of decarburization five is mainly aromatic component, carries out depth into product separation and purification unit isolated
Aromatic hydrocarbon product 10.
Further, step (5) the catalysis drying gas aromatized catalyst is the Mo/ZSM-5 catalyst of additive modification, its
In：
The weight content of ZSM-5 molecular sieve is 90wt%,
The weight content of metal Mo oxides is 10wt%,
The weight content of modified additive is 10wt%,
Remaining is aluminum oxide.
Further, the modified additive of catalyst is P.
Further, the first reactor 4 and second reactor 5 in step (5) is in parallel, is switched using reactor in operation
Operation, a reactor normal reaction production, another reactor carries out catalyst regenerative operation.
Further, the reaction condition of first reactor 4 and second reactor 5 is：
Reaction pressure is 1.0MPa,
Reaction temperature is 650 DEG C,
Reaction volume air speed is 2000h-1,
Catalyst one way service cycle is in 400h.
Further, the catalyst after inactivating in first reactor 4 and second reactor 5 is entered using oxygen containing inert gas
Row regeneration, wherein
Oxygen content is 5.0vol%,
Regeneration temperature is 500 DEG C,
Pressure is 3.0MPa,
Gas/agent volume ratio is 1000.
Further, inert gas is nitrogen.
Specific embodiment 3
As shown in figure 1, a kind of method for preparing aromatic hydrocarbons by dry gas, comprises the following steps：
(1) depth fine de-sulfur
(11) first grade desulfurizing
Catalysis drying gas are sent into into normal temperature iron oxide fine de-hydrogen sulfide column, hydrogen sulfide in dry gas is taken off to below 1ml/L, its
In：Normal temperature iron oxide fine de-hydrogen sulfide column operating condition is：
30 DEG C of operating temperature,
Volume space velocity 1000h-1；
(12) two-grade desulfurizing
The de- small molecule mercaptan tower of normal temperature NaX molecular sieves will be sent into through the catalysis drying gas of first grade desulfurizing, by catalysis drying gas
Mercaptan is taken off to below 1ml/L, and the operating condition of the de- small molecule mercaptan tower of normal temperature NaX molecular sieves is：
30 DEG C of operating temperature,
Volume space velocity 1000h-1；
(2) deoxygenation
By the catalysis drying gas after secondary desulfuration by loading CuO-MnO2Remove in the deoxidation tower of bimetallic deoxidier
Oxygen, oxygen content in catalysis drying gas is removed to less than 10ml/L, CuO and MnO2Active component weight content be 70～
90%, remaining is aluminum oxide, CuO and MnO2Ratio be 2：10, load CuO-MnO2The operation of the deoxidation tower of bimetallic deoxidier
Condition is：
Volume space velocity 2500h-1,
Operating temperature is normal temperature；
(3) it is dried
To be adsorbed by drying by loading the dehydrating tower of 3A molecular sieves through the catalysis drying gas of deoxygenation, drying condition is：
Volume space velocity 1500h-1, water content in dry gas is down to below 1ml/l by normal temperature；
(4) will first send into raw material-product exchanger 2 through dry purifying and catalyzing dry gas raw material 1 to exchange heat, be then re-fed into
Raw materials furnace and heating 3 is heated to 480 DEG C；
(5) by step (4), through the catalysis drying gas of heating, alternately being passed through first reactor 4 or second reactor 5 carries out virtue
Structureization reaction obtains product, wherein：
Catalysis drying gas aromatized catalyst has been loaded in first reactor 4 and second reactor 5；
(6) product that step (5) is obtained first is sent in raw material-product exchanger 2 and is condensed, be cooled to 45 DEG C
Afterwards, then it is sent to knockout drum 6 and obtains liquid product and gas-phase product, liquid product is sent into de- through BTX aromatics pump 7
The tower 8 of carbon five, the hydro carbons in liquid product less than carbon five is separated from tower top, and is become with the gaseous component Jing in knockout drum 6
Pressure adsorbent equipment 9 isolates high-purity hydrogen 11, and remaining small molecule hydrocarbon component together mixes feeding raw materials furnace and heating 3 with raw material
Freshening；
(7) bottom of the tower 8 of decarburization five is mainly aromatic component, carries out depth into product separation and purification unit isolated
Aromatic hydrocarbon product 10.
Further, step (5) the catalysis drying gas aromatized catalyst is the Mo/ZSM-5 catalyst of additive modification, its
In：
The weight content of ZSM-5 molecular sieve is 50wt%,
The weight content of metal Mo oxides is 5wt%,
The weight content of modified additive is 0.5wt%,
Remaining is aluminum oxide.
Further, the modified additive of catalyst is F.
Further, the first reactor 4 and second reactor 5 in step (5) is in parallel, is switched using reactor in operation
Operation, a reactor normal reaction production, another reactor carries out catalyst regenerative operation.
Further, the reaction condition of first reactor 4 and second reactor 5 is：
Reaction pressure is 0.5MPa,
Reaction temperature is 500 DEG C,
Reaction volume air speed is 500h-1,
Catalyst one way service cycle is in 300h.
Further, the catalyst after inactivating in first reactor 4 and second reactor 5 is entered using oxygen containing inert gas
Row regeneration, wherein
Oxygen content is 3.0vol%,
Regeneration temperature is 450 DEG C,
Pressure is 1.5MPa,
Gas/agent volume ratio is 600.
Further, inert gas is nitrogen.
Specific embodiment 4
It is roughly the same with specific embodiment 3, differ only in：
Step (5) the catalysis drying gas aromatized catalyst is the Mo/ZSM-5 catalyst of additive modification, wherein：
The weight content of ZSM-5 molecular sieve is 70wt%,
The weight content of metal Mo oxides is 8wt%,
The weight content of modified additive is 3wt%,
Remaining is aluminum oxide.
The modified additive of catalyst is Cl.
Specific embodiment 5
It is roughly the same with specific embodiment 3, differ only in：
Step (5) the catalysis drying gas aromatized catalyst is the Mo/ZSM-5 catalyst of additive modification, wherein：
The weight content of ZSM-5 molecular sieve is 60wt%,
The weight content of metal Mo oxides is 6wt%,
The weight content of modified additive is 2wt%,
Remaining is aluminum oxide.
The modified additive of catalyst is Zr.
Specific embodiment 6
It is roughly the same with specific embodiment 1, differ only in：
The modified additive of catalyst is Cr.
Specific embodiment 7
It is roughly the same with specific embodiment 2, differ only in：
The modified additive of catalyst is Zn.
Specific embodiment 8
It is roughly the same with specific embodiment 3, differ only in：
The modified additive of catalyst is La.
Specific embodiment 9
It is roughly the same with specific embodiment 1, differ only in：
The modified additive of catalyst is Ce.
Specific embodiment 10
It is roughly the same with specific embodiment 2, differ only in：
The modified additive of catalyst is the mixture in B, P, F, Cl, Zr, Cr, Zn, La and the Ce for wait mass ratio.
Embodiments of the present invention are elaborated above.But the present invention is not limited to above-mentioned embodiment,
In the ken that art those of ordinary skill possesses, can be doing on the premise of without departing from present inventive concept
Go out various change.
Claims (8)
1. a kind of method that aromatic hydrocarbons is prepared by dry gas, it is characterised in that comprise the following steps：
(1) depth fine de-sulfur
(11) first grade desulfurizing
Catalysis drying gas are sent into into normal temperature iron oxide fine de-hydrogen sulfide column, hydrogen sulfide in dry gas is taken off to below 1ml/L, wherein：Often
Warm iron oxide fine de-hydrogen sulfide column operating condition is：
20～40 DEG C of operating temperature,
500～1500h of volume space velocity-1；
(12) two-grade desulfurizing
The de- small molecule mercaptan tower of normal temperature NaX molecular sieves will be sent into through the catalysis drying gas of first grade desulfurizing, by mercaptan in catalysis drying gas
Take off to below 1ml/L, the operating condition of the de- small molecule mercaptan tower of normal temperature NaX molecular sieves is：
20～40 DEG C of operating temperature,
500～1500h of volume space velocity-1；
(2) deoxygenation
By the catalysis drying gas after secondary desulfuration by loading CuO-MnO2Oxygen is removed in the deoxidation tower of bimetallic deoxidier,
Oxygen content in catalysis drying gas is removed to less than 10ml/L, CuO and MnO2Active component weight content is 70～90%, remaining
For aluminum oxide, CuO and MnO2Ratio be (1～3)：10, load CuO-MnO2The operating condition of the deoxidation tower of bimetallic deoxidier
For：
2000～3000h of volume space velocity-1,
Operating temperature is normal temperature；
(3) it is dried
To be adsorbed by drying by loading the dehydrating tower of 3A molecular sieves through the catalysis drying gas of deoxygenation, drying condition is：
1000～2000h of volume space velocity-1, water content in dry gas is down to below 1ml/l by normal temperature；
(4) raw material-product exchanger heat exchange will be first sent into through dry purifying and catalyzing dry gas raw material, is then re-fed into raw material and adds
Hot stove heat is to 400～550 DEG C；
(5) by step (4) through the catalysis drying gas of heating be alternately passed through first reactor or second reactor to carry out aromatisation anti-
Product should be obtained, wherein：
Catalysis drying gas aromatized catalyst has been loaded in first reactor and second reactor；
(6) product that step (5) is obtained first is sent in raw material-product exchanger and is condensed, be cooled to 30～60 DEG C
Afterwards, then it is sent to knockout drum and obtains liquid product and gas-phase product, liquid product is pumped into decarburization through BTX aromatics
Five towers, the hydro carbons in liquid product less than carbon five is separated from tower top, and is inhaled with the gaseous component Jing transformations in knockout drum
Adsorption device isolates high-purity hydrogen, and remaining small molecule hydrocarbon component together mixes feeding raw materials furnace and heating freshening with raw material；
(7) bottom of the tower of decarburization five is mainly aromatic component, and into product separation and purification unit the isolated aromatic hydrocarbons of depth is carried out
Product.
2. a kind of method that aromatic hydrocarbons is prepared by dry gas according to claim 1, it is characterised in that step (5) is described to urge
Change Mo/ZSM-5 catalyst of the dry gas aromatized catalyst for additive modification, wherein：
The weight content of ZSM-5 molecular sieve is 20～90wt%,
The weight content of metal Mo oxides is 0.1～10wt%,
The weight content of modified additive is 0.1～10wt%,
Remaining is aluminum oxide.
3. a kind of method that aromatic hydrocarbons is prepared by dry gas according to claim 2, it is characterised in that step (5) is described to urge
Change Mo/ZSM-5 catalyst of the dry gas aromatized catalyst for additive modification, wherein：
The weight content of ZSM-5 molecular sieve is 50～70wt%,
The weight content of metal Mo oxides is 5～8wt%,
The weight content of modified additive is 0.5～3wt%,
Remaining is aluminum oxide.
4. a kind of method that aromatic hydrocarbons is prepared by dry gas according to claim 3, it is characterised in that the modified of catalyst helps
Agent for B, P, F, Cl, Zr, Cr, Zn, La and Ce in one or more.
5. a kind of method that aromatic hydrocarbons is prepared by dry gas according to claim 1, it is characterised in that in step (5)
One reactor and second reactor are in parallel, and reactor handover operation is adopted in operation, and a reactor normal reaction production is another
Individual reactor carries out catalyst regenerative operation.
6. a kind of method that aromatic hydrocarbons is prepared by dry gas according to claim 5, it is characterised in that first reactor and
The reaction condition of two reactors is：
Reaction pressure is 0.1～1.0MPa,
Reaction temperature is 500～650 DEG C,
Reaction volume air speed is 500～2000h-1,
Catalyst one way service cycle is in 200～400h.
7. a kind of method that aromatic hydrocarbons is prepared by dry gas according to claim 5, it is characterised in that first reactor and
Catalyst after inactivating in two reactors is regenerated using oxygen containing inert gas, wherein
Oxygen content is 0.5～5.0vol%,
Regeneration temperature is 400～500 DEG C,
Pressure is 0.1～3.0MPa,
Gas/agent volume ratio is 250～1000.
8. a kind of method that aromatic hydrocarbons is prepared by dry gas according to claim 7, it is characterised in that inert gas is nitrogen
Gas.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1183398A (en) * | 1996-11-25 | 1998-06-03 | 中国科学院大连化学物理研究所 | Process for preparing aromatic hydrocarbon from catalytic cracking tail gas in absence of oxygen |
| CN201390716Y (en) * | 2009-04-08 | 2010-01-27 | 大庆油田有限责任公司 | Aromatization catalytic reaction experimental device |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1183398A (en) * | 1996-11-25 | 1998-06-03 | 中国科学院大连化学物理研究所 | Process for preparing aromatic hydrocarbon from catalytic cracking tail gas in absence of oxygen |
| CN201390716Y (en) * | 2009-04-08 | 2010-01-27 | 大庆油田有限责任公司 | Aromatization catalytic reaction experimental device |
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