CN114437773B - Method for preparing aromatic hydrocarbon by coupling synthetic gas with naphtha - Google Patents

Method for preparing aromatic hydrocarbon by coupling synthetic gas with naphtha Download PDF

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CN114437773B
CN114437773B CN202011115892.1A CN202011115892A CN114437773B CN 114437773 B CN114437773 B CN 114437773B CN 202011115892 A CN202011115892 A CN 202011115892A CN 114437773 B CN114437773 B CN 114437773B
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catalyst
molecular sieve
reaction
zsm
auxiliary agent
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CN114437773A (en
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王海洋
张信伟
李�杰
李红营
郭智芳
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Sinopec Dalian Petrochemical Research Institute Co ltd
China Petroleum and Chemical Corp
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China Petroleum and Chemical Corp
Sinopec Dalian Research Institute of Petroleum and Petrochemicals
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G61/00—Treatment of naphtha by at least one reforming process and at least one process of refining in the absence of hydrogen
    • C10G61/10—Treatment of naphtha by at least one reforming process and at least one process of refining in the absence of hydrogen processes also including other conversion steps
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/40—Characteristics of the process deviating from typical ways of processing
    • C10G2300/4006—Temperature
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/40—Characteristics of the process deviating from typical ways of processing
    • C10G2300/4012—Pressure
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/40—Characteristics of the process deviating from typical ways of processing
    • C10G2300/4018—Spatial velocity, e.g. LHSV, WHSV
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/70—Catalyst aspects
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/30—Aromatics
    • 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
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Catalysts (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The application discloses a method for preparing aromatic hydrocarbon from synthesis gas, which comprises the following steps: (1) contacting the synthesis gas with an olefin catalyst for reaction; (2) Mixing the material flow reacted in the step (1) with naphtha, and reacting under the action of a catalyst containing ZSM-5 molecular sieve; (3) separating the reacted flow in the step (2) to obtain aromatic hydrocarbon. The method can produce high-added-value aromatic hydrocarbon products in a more yield manner.

Description

Method for preparing aromatic hydrocarbon by coupling synthetic gas with naphtha
Technical Field
The application relates to a method for preparing aromatic hydrocarbon by coupling synthetic gas with naphtha, in particular to a method for preparing aromatic hydrocarbon by coupling synthetic gas with naphtha with high yield.
Background
With the development of society and the improvement of economic level, the demand for clean liquid fuels and chemicals (aromatic hydrocarbons) has increased year by year. Coal resources in China are rich, and synthesis gas (CO and H) is obtained by gasifying coal under the current situation of lack of petroleum resources in China 2 ) The product obtained by the synthesis gas through the Fischer-Tropsch synthesis route follows Anderson-Schulz-Flory (ASF) distribution, has wide carbon number distribution, has great difficulty in selectively controlling high-added-value products, and has great limitation in application. The technical route for preparing aromatic hydrocarbon by two-stage or multi-stage reaction of synthetic gas has higher cost.
Patent CN201610965244.2 discloses a catalyst for preparing light aromatic hydrocarbon from synthetic gas with high selectivity and a preparation method thereof, wherein the catalyst comprises 20-60% of modified zeolite molecular sieve and 40-80% of zirconium-containing composite oxide. The preparation method comprises the following steps: adding the zirconium-containing composite oxide into a solvent, and performing ultrasonic dispersion to obtain a solution A; adding a modified zeolite molecular sieve into the solution A; filtering the mixture after ultrasonic dispersion, washing, and drying the obtained filter cake; grinding the dried sample into powder; and roasting the obtained powder sample, wherein the obtained sample is the catalyst for preparing the light aromatic hydrocarbon from the synthesis gas with high selectivity.
Patent CN201711133394.8 discloses a process for preparing aromatic hydrocarbons from synthesis gas, which comprises: a) Contacting a feed stream comprising synthesis gas with a catalyst in a reaction zone under reaction conditions sufficient to convert at least a portion of the feed to obtain a reaction effluent; b) Separating the reaction effluent to obtain at least a recycle stream comprising gaseous hydrocarbons having 1-4 carbon atoms and unconverted synthesis gas and a liquid stream comprising hydrocarbons having greater than or equal to 5 carbon atoms; c) Returning said recycle stream to said reaction zone; and d) separating the aromatic hydrocarbon product from the liquid stream, wherein the catalyst comprises at least one of an inert support limited domain highly dispersed metal oxide material, an acidic molecular sieve, and optionally graphite powder and a dispersing agent.
Patent CN20170917428.6 discloses a core-shell catalyst whose core is HZSM-5 molecular sieve, modified ZSM-5 molecular sieve in which all or part of H in HZSM-5 molecular sieve is replaced by (non) metal element as defined in the specification or mixture thereof, shell is selected from carbon film, silicalite-1, MCM-41, SBA-15, KIT-6, MSU series, silica, graphene, carbon nanotube, metal organic framework MOF, graphite, activated carbon, metal oxide film.
In the preparation method, during the process of directly preparing aromatic hydrocarbon by one-stage reaction of the synthetic gas, the main reaction is hydrocarbon preparation (Fischer-Tropsch reaction) -aromatization reaction of the synthetic gas or methanol preparation-aromatization reaction of the synthetic gas, the selectivity limit of the product of the Fischer-Tropsch synthesis leads to low conversion rate of the synthetic gas, the final aromatic hydrocarbon content is low, and the strong exothermic reaction of the methanol leads to poor stability of the catalyst and easy sintering and inactivation.
Disclosure of Invention
In order to overcome the defects in the prior art, the application provides a method for preparing aromatic hydrocarbon by coupling synthesis gas with naphtha, which can produce high-added-value aromatic hydrocarbon products in a more-yield manner.
A method for preparing aromatic hydrocarbon from synthesis gas, comprising the following steps:
(1) The synthetic gas is contacted with an olefin catalyst for reaction;
(2) Mixing the material flow reacted in the step (1) with naphtha, and reacting under the action of a catalyst containing ZSM-5 molecular sieve;
(3) And (3) separating the reacted material in the step (2) to obtain aromatic hydrocarbon.
In the above method, the reaction conditions in step (1) are as follows: the reaction temperature is 200-800 ℃, preferably 300-500 ℃; the reaction pressure is 0.1-5Mpa, preferably 1-3Mpa; the integral volume space velocity of the synthesis gas is 500-20000h -1 Preferably 1000-10000h -1 。
In the above method, the olefin-producing catalyst in the step (1) comprises an active component, an auxiliary agent and a carrier, wherein the active component is one or more of Fe, co, ni monoatomic metal and/or metal oxide thereof, preferably Fe oxide; the auxiliary agent is one or more of K, mn, na, cu, B and/or oxides thereof, preferably K; the carrier is one or more of silicon dioxide, activated carbon, aluminum oxide, amorphous silicon aluminum, titanium oxide, Y-type molecular sieve and A-type molecular sieve, preferably silicon dioxide. The active component is 5-40wt.%, preferably 10-30 wt wt.%, and the additive is 1-10 wt wt.%, preferably 2-5 wt wt.%, and the carrier is 30-90 wt wt.%, preferably 40-70 wt wt.%, calculated as oxides, based on the weight of the final catalyst. The olefin-producing catalyst may be spherical, bar-shaped, or the like as required, and the molded catalyst contains a binder, typically alumina.
In the above method, the reaction conditions in step (2) are as follows: the reaction temperature is 300-700 ℃, preferably 350-600 ℃; the reaction pressure is 0.1-5Mpa, preferably 0.2-0.8Mpa; the space velocity of the naphtha liquid feed is 0.1 to 10 hours -1 Preferably 0.5-2h -1 。
In the method, the catalyst containing ZSM-5 molecular sieve in the step (2) is a molded catalyst, the catalyst is in the shape of sphere, bar and clover, the molded catalyst contains a binder, and the binder can be alumina.
In the above method, the ZSM-5-containing molecular sieve catalyst in step (2) may contain an auxiliary agent, where the auxiliary agent is one or more elements in IIIA, IVA, IIA, IVB, VIIIB, VIA, VA, and preferably one or more elements in B, P, al, si, mg, zr, ni.
In the above process, the ZSM-5 containing molecular sieve catalyst described in step (2) optionally comprises from 0.1 to 30%, preferably from 0.5 to 20%, more preferably from 5 to 10% by weight of the final catalyst of adjunct oxide; the ZSM-5 molecular sieve is present in the catalyst in an amount of from 30% to 100%, preferably from 40% to 90%, more preferably from 50% to 80%, still more preferably from 60% to 70%.
In the above process, the volume content of olefin in the reaction effluent of the step (1) is controlled to be 10-80%, preferably 50-70%, and the proportion of olefin having carbon number greater than 3 is controlled to be 30-90%, preferably 70-80%. The coupled aromatization reaction of the material containing proper olefin and naphtha hydrocarbon molecules is controlled, the conversion efficiency of hydrocarbon molecules is promoted, and the yield and selectivity of aromatic hydrocarbon are improved.
In the above process, the carbon monoxide volume content in the feed to step (2) is controlled to be 0.1% to 10%, preferably 0.5% to 2%. The selectivity of aromatic hydrocarbon, especially the selectivity of BTX with high added value, can be further improved by controlling a certain amount of carbon monoxide in the material; the generation of coke on the catalyst is inhibited by a small amount of unreacted synthesis gas, the reaction operation period is greatly prolonged, and the service life of the catalyst is prolonged.
The ZSM-5 containing molecular sieve catalyst employed in certain embodiments of the application has a proportion of acid content > 350 ℃ of less than 15%, preferably less than 10, more preferably less than 5, still more preferably from 0.5% to 5%, and in particular may be 1%, 2%, 3%, 4% of the total acid content below 450 ℃, and may be selected from commercial products or prepared by a process comprising the steps of: (1) selecting or self-preparing an aromatization catalyst; (2) Treating the aromatization catalyst in step (1) to adsorb compounds containing basic sites at the acidic sites in the catalyst; (3) And (3) selectively desorbing and recovering part of acid sites from the material in the step (2), and optionally drying and roasting to obtain the final aromatization catalyst.
Compared with the prior art, the method for preparing aromatic hydrocarbon by coupling the synthetic gas with naphtha can remarkably improve the yield of aromatic hydrocarbon, and particularly improve the selectivity of BTX with high added value.
Detailed Description
The operation and effects of the method of the present application will be further described with reference to examples and comparative examples, but the following examples do not limit the method of the present application. In the application, if the catalyst composition does not meet 100% by mass, the balance is binder alumina.
Example 1
(1) Synthesis gas (H) 2 Co=2) with a catalyst for the production of olefins from synthesis gas under reaction conditions as follows: the reaction temperature is 300 ℃, the reaction pressure is 1Mpa, and the volume space velocity of the synthesis gas is 1000h -1 The catalyst composition is as follows: 10% of Fe oxide, 2% of K based on simple substance and 40% of silicon dioxide;
(2) Mixing the material flow reacted in the step (1) with naphtha, and contacting the material flow with a catalyst containing ZSM-5 molecular sieve to react under the following reaction conditions: the reaction temperature is 350 ℃, the reaction pressure is 0.2Mpa, and the volume space velocity of the material flow after the reaction in the step (1) enters the reaction area in the step (2) for 5h -1 Naphtha liquid feed space velocity of 0.5 h -1 The catalyst composition is as follows: ZSM-5 content of 60% and alumina content of 5%;
(3) And (3) separating the reacted material flow in the step (2) to obtain aromatic hydrocarbon, wherein the aromatic hydrocarbon yield and the BTX content in the liquid product are shown in Table 1.
Example 2
(1) Synthesis gas (H) 2 Co=2) with a catalyst for the production of olefins from synthesis gas under reaction conditions as follows: the reaction temperature is 500 ℃, the reaction pressure is 3Mpa, and the volume space velocity of the synthesis gas is 10000h -1 The catalyst composition is as follows: 30% of Fe oxide, 5% of K in terms of simple substance and 70% of silicon dioxide;
(2) Mixing the material flow reacted in the step (1) with naphtha, and contacting the material flow with a catalyst containing ZSM-5 molecular sieve to react under the following reaction conditions: the reaction temperature is 600 ℃, the reaction pressure is 0.8Mpa, and the volume space velocity of the material flow after the reaction in the step (1) enters the reaction area in the step (2) for 10h -1 Naphtha liquid feed space velocity 2h -1 The catalyst composition is as follows: ZSM-5 content of 70%, alumina content of 10%;
(3) And (3) separating the reacted material flow in the step (2) to obtain aromatic hydrocarbon, wherein the aromatic hydrocarbon yield and the BTX content in the liquid product are shown in Table 1.
Example 3
(1) Synthesis gas (H) 2 Co=2) with a catalyst for the production of olefins from synthesis gas under reaction conditions as follows: the reaction temperature is 400 ℃, the reaction pressure is 2Mpa, and the volume space velocity of the synthesis gas is 5000h -1 The catalyst composition is as follows: 20% of Fe oxide, 3% of K in terms of simple substance and 50% of silicon dioxide;
(2) Mixing the material flow reacted in the step (1) with naphtha, and contacting the material flow with a catalyst containing ZSM-5 molecular sieve to react under the following reaction conditions: the reaction temperature is 450 ℃, the reaction pressure is 0.5Mpa, and the volume space velocity of the material flow after the reaction in the step (1) enters the reaction area in the step (2) for 8h -1 Naphtha liquid feed space velocity 1h -1 The catalyst composition is as follows: the ZSM-5 content is 65 percent, and the alumina content is 8 percent.
(3) And (3) separating the reacted material flow in the step (2) to obtain aromatic hydrocarbon, wherein the aromatic hydrocarbon yield and the BTX content in the liquid product are shown in Table 1.
Example 4
(1) Synthesis gas (H) 2 Co=2) with a catalyst for the production of olefins from synthesis gas under reaction conditions as follows: the reaction temperature is 300 ℃, the reaction pressure is 1Mpa, and the volume space velocity of the synthesis gas is 1000h -1 The catalyst composition is as follows: 10% of Fe oxide, 2% of K based on simple substance and 40% of silicon dioxide;
(2) The effluent stream after the reaction of step (1) contains 50% of olefins, wherein the proportion of olefins with carbon number greater than 3 is 70%, the unreacted synthesis gas content is 1% and the CO content is 0.5%. The material flow is mixed with naphtha to be contacted with a ZSM-5 molecular sieve catalyst for reaction under the following reaction conditions: the reaction temperature is 350 ℃, the reaction pressure is 0.2Mpa, and the volume space velocity of the material flow after the reaction in the step (1) enters the reaction area in the step (2) for 5h -1 Naphtha liquid feed space velocity of 0.5 h -1 The catalyst composition is as follows: ZSM-5 content of 60% and alumina content of 5%;
(3) And (3) separating the reacted material flow in the step (2) to obtain aromatic hydrocarbon, wherein the aromatic hydrocarbon yield and the BTX content in the liquid product are shown in Table 1.
Example 5
(1) Synthesis gas (H) 2 Co=2) with a catalyst for the production of olefins from synthesis gas under reaction conditions as follows: the reaction temperature is 300 ℃, the reaction pressure is 1Mpa, and the volume space velocity of the synthesis gas is 1000h -1 The catalyst composition is as follows: 10% of Fe oxide, 2% of K based on simple substance and 40% of silicon dioxide;
(2) The effluent stream after the reaction of step (1) contains 70% of olefins, wherein the proportion of olefins with carbon number greater than 3 is 80%, 5% of unreacted synthesis gas and 2% of CO. The material flow is mixed with naphtha to be contacted with a ZSM-5 molecular sieve catalyst for reaction under the following reaction conditions: the reaction temperature is 350 ℃, the reaction pressure is 0.2Mpa, and the volume space velocity of the material flow after the reaction in the step (1) enters the reaction area in the step (2) for 5h -1 Naphtha liquid feed space velocity of 0.5 h -1 The catalyst composition is as follows: ZSM-5 content of 60% and alumina content of 5%;
(3) And (3) separating the reacted material flow in the step (2) to obtain aromatic hydrocarbon, wherein the aromatic hydrocarbon yield and the BTX content in the liquid product are shown in Table 1.
Example 6
(1) Synthesis gas (H) 2 Co=2) with a catalyst for the production of olefins from synthesis gas under reaction conditions as follows: the reaction temperature is 300 ℃, the reaction pressure is 1Mpa, and the volume space velocity of the synthesis gas is 1000h -1 The catalyst composition is as follows: 10% of Fe oxide, 2% of K based on simple substance and 40% of silicon dioxide. The content of olefin in the effluent stream after the reaction is finished is 20%, wherein the proportion of olefin with carbon number more than 3 is 70%;
(2) The effluent stream after the reaction of step (1) contains 20% of olefins, wherein the proportion of olefins with carbon number greater than 3 is 70%, the unreacted synthesis gas content is 1%, and the CO content is 0.5%. The material flow is mixed with naphtha to be contacted with a ZSM-5 molecular sieve catalyst for reaction under the following reaction conditions: the reaction temperature is 350 ℃, the reaction pressure is 0.2Mpa,the material flow after the reaction of the step (1) enters the volume space velocity of the reaction area of the step (2) for 5h -1 Naphtha liquid feed space velocity of 0.5 h -1 The catalyst composition is as follows: the content of ZSM-5 is 60%, the content of aluminum oxide is 5%, and the proportion of the acid quantity of the aromatization catalyst in the second reaction zone below 350 ℃ to the total acid quantity below 450 ℃ is controlled to be 96%;
(3) And (3) separating the reacted material flow in the step (2) to obtain aromatic hydrocarbon, wherein the aromatic hydrocarbon yield and the BTX content in the liquid product are shown in Table 1.
Example 7
(1) Synthesis gas (H) 2 Co=2) with a catalyst for the production of olefins from synthesis gas under reaction conditions as follows: the reaction temperature is 300 ℃, the reaction pressure is 1Mpa, and the volume space velocity of the synthesis gas is 1000h -1 The catalyst composition is as follows: 10% of Fe oxide, 2% of K based on simple substance and 40% of silicon dioxide. The content of olefin in the effluent stream after the reaction is finished is 20%, wherein the proportion of olefin with carbon number more than 3 is 70%;
(2) The effluent stream after the reaction of step (1) contains 20% of olefins, wherein the proportion of olefins with carbon number greater than 3 is 70%, the unreacted synthesis gas content is 1%, and the CO content is 0.5%. The material flow is mixed with naphtha to be contacted with a ZSM-5 molecular sieve catalyst for reaction under the following reaction conditions: the reaction temperature is 350 ℃, the reaction pressure is 0.2Mpa, and the volume space velocity of the material flow after the reaction in the step (1) enters the reaction area in the step (2) for 5h -1 Naphtha liquid feed space velocity of 0.5 h -1 The catalyst composition is as follows: the content of ZSM-5 is 60%, the content of aluminum oxide is 5%, and the proportion of the total acid quantity of the second reaction zone aromatization catalyst below 350 ℃ to the total acid quantity below 450 ℃ is controlled to be 99%;
(3) And (3) separating the reacted material flow in the step (2) to obtain aromatic hydrocarbon, wherein the aromatic hydrocarbon yield and the BTX content in the liquid product are shown in Table 1.
Comparative example 1
In comparison to example 1, no naphtha was passed, and other process parameters and catalyst compositions were the same as those described in example 1.
Comparative example 2
The synthesis gas and naphtha were fed directly to the second reaction zone and the other process parameters and catalyst composition were the same as those described in example 1.
TABLE 1 product Properties

Claims (16)

1. A method for preparing aromatic hydrocarbon from synthesis gas is characterized by comprising the following steps: the method comprises the following steps:
(1) The synthetic gas is contacted with an olefin catalyst for reaction;
(2) Mixing the material flow reacted in the step (1) with naphtha, and reacting under the action of a catalyst containing ZSM-5 molecular sieve;
(3) Separating the reacted material in the step (2) to obtain aromatic hydrocarbon;
controlling the volume content of olefin in the reaction effluent of the step (1) to be 20-80%, wherein the proportion of olefin with carbon number more than 3 is 70-90%; controlling the volume content of carbon monoxide in the feed of the step (2) to be 0.1% -10%; the proportion of the acid quantity of ZSM-5 molecular sieve catalyst less than 350 ℃ to the total acid quantity below 450 ℃ is 96% or 99%.
2. The method according to claim 1, characterized in that: the olefin preparation catalyst in the step (1) comprises an active component, an auxiliary agent and a carrier, wherein the active component is one or more of Fe, co and Ni monoatomic metals and/or metal oxides thereof; the auxiliary agent is one or more of K, mn, na, cu, B and/or oxides thereof; the carrier is one or more of silicon dioxide, active carbon, aluminum oxide, amorphous silica-alumina, titanium oxide, Y-type molecular sieve and A-type molecular sieve, wherein the weight of the active component is 5-40wt% calculated by oxide, the additive is 1-10 wt% calculated by simple substance, and the carrier is 30-90 wt%.
3. The method according to claim 2, characterized in that: the olefin preparation catalyst in the step (1) comprises an active component, an auxiliary agent and a carrier, wherein the active component is Fe oxide; the auxiliary agent is K; the carrier is silicon dioxide, wherein the active component is 5-40wt% based on oxide, the auxiliary agent is 1-10 wt% based on simple substance, and the carrier is 40-70 wt%.
4. The method according to claim 1, characterized in that: the reaction conditions of the step (1) are as follows: the reaction temperature is 200-800 ℃; the reaction pressure is 0.1-5Mpa; the integral volume space velocity of the synthesis gas is 500-20000h -1 。
5. The method according to claim 4, wherein: the reaction conditions of the step (1) are as follows: the reaction temperature is 300-
500 ℃; the reaction pressure is 1-3Mpa; the integral volume space velocity of the synthesis gas is 1000-10000h -1 。
6. The method according to claim 1, characterized in that: the reaction conditions of step (2) are as follows: reaction temperature 300-
700 ℃; the reaction pressure is 0.1-5Mpa; the space velocity of the naphtha liquid feed is 0.1 to 10 hours -1 。
7. The method according to claim 6, wherein: the reaction conditions of step (2) are as follows: reaction temperature of 350-
600 ℃; the reaction pressure is 0.2-0.8Mpa; naphtha liquid feeding airspeed of 0.5-2h -1 。
8. The method according to claim 1, characterized in that: the ZSM-5 molecular sieve-containing catalyst in the step (2) is a molded catalyst, the catalyst is in the shape of a sphere, a bar or a clover, and the molded catalyst contains a binder.
9. The method according to claim 8, wherein: the ZSM-5 molecular sieve-containing catalyst in the step (2) contains an auxiliary agent which is one or more elements in IIIA, IVA, IIA, IVB, VIIIB, VIA, VA.
10. The method according to claim 9, wherein: the auxiliary agent is one or more of B, P, al, si, mg, zr, ni.
11. The method according to claim 1, characterized in that: the ZSM-5 molecular sieve containing catalyst in step (2) contains 0.1% -30% of optional auxiliary agent by weight of the final catalyst, 30% -100% of ZSM-5 molecular sieve in the catalyst, and the total weight of the catalyst is 100%.
12. The method according to claim 11, wherein: the ZSM-5 molecular sieve-containing catalyst in the step (2) contains 0.5 to 20 percent of optional auxiliary agent in terms of oxide in the catalyst and 40 to 90 percent of ZSM-5 molecular sieve in the catalyst based on the weight of the final catalyst.
13. The method according to claim 11, wherein: the ZSM-5 molecular sieve-containing catalyst in the step (2) contains 5 to 10 percent of optional auxiliary agent in terms of oxide in the catalyst and 50 to 80 percent of ZSM-5 molecular sieve in the catalyst based on the weight of the final catalyst.
14. The method according to claim 11, wherein: the ZSM-5 molecular sieve containing catalyst described in step (2) comprises 60% to 70% of ZSM-5 molecular sieve based on the weight of the final catalyst.
15. The method according to claim 1, characterized in that: controlling the volume content of olefin in the reaction effluent of the step (1) to be 50-70%, wherein the proportion of olefin with carbon number more than 3 is 70-80%.
16. The method according to claim 1, characterized in that: controlling the volume content of carbon monoxide in the feed of the step (2) to be 0.5-2%.
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CN109794283A (en) * 2017-11-15 2019-05-24 中国科学院大连化学物理研究所 A method of by the direct preparing aromatic hydrocarbon of synthesis gas
CN111205159A (en) * 2020-01-17 2020-05-29 大连凯信科技研发有限公司 Method for preparing low-carbon olefin from synthesis gas

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WO2004081147A2 (en) * 2003-03-07 2004-09-23 Conocophillips Company Octane improvement of a hydrocarbon stream
US20100160700A1 (en) * 2008-12-18 2010-06-24 Chevron U.S.A. Inc. Process and catalysts for reforming fisher tropsch naphthas to aromatics

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CN109794283A (en) * 2017-11-15 2019-05-24 中国科学院大连化学物理研究所 A method of by the direct preparing aromatic hydrocarbon of synthesis gas
CN111205159A (en) * 2020-01-17 2020-05-29 大连凯信科技研发有限公司 Method for preparing low-carbon olefin from synthesis gas

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