CN114437772A - Method for preparing gasoline by coupling synthesis gas with naphtha - Google Patents
Method for preparing gasoline by coupling synthesis gas with naphtha Download PDFInfo
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- CN114437772A CN114437772A CN202011115274.7A CN202011115274A CN114437772A CN 114437772 A CN114437772 A CN 114437772A CN 202011115274 A CN202011115274 A CN 202011115274A CN 114437772 A CN114437772 A CN 114437772A
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- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 49
- 239000003502 gasoline Substances 0.000 title claims abstract description 36
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 title claims abstract description 34
- 230000008878 coupling Effects 0.000 title claims abstract description 9
- 238000010168 coupling process Methods 0.000 title claims abstract description 9
- 238000005859 coupling reaction Methods 0.000 title claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims description 125
- 239000003054 catalyst Substances 0.000 claims description 58
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 51
- 239000007789 gas Substances 0.000 claims description 44
- 238000005899 aromatization reaction Methods 0.000 claims description 20
- 229910052739 hydrogen Inorganic materials 0.000 claims description 19
- 239000001257 hydrogen Substances 0.000 claims description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 16
- 239000002808 molecular sieve Substances 0.000 claims description 13
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 13
- 239000002253 acid Substances 0.000 claims description 9
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 9
- 229910052725 zinc Inorganic materials 0.000 claims description 9
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- 239000012752 auxiliary agent Substances 0.000 claims description 4
- 229910052796 boron Inorganic materials 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000011959 amorphous silica alumina Substances 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 abstract description 6
- 239000000047 product Substances 0.000 description 12
- 239000011701 zinc Substances 0.000 description 10
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 7
- 239000005751 Copper oxide Substances 0.000 description 7
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 7
- 229910000431 copper oxide Inorganic materials 0.000 description 7
- 239000002002 slurry Substances 0.000 description 5
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000000446 fuel Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- -1 SAPO-11 Chemical compound 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Classifications
-
- 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
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/30—Physical properties of feedstocks or products
- C10G2300/305—Octane number, e.g. motor octane number [MON], research octane number [RON]
-
- 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
- C10G2400/02—Gasoline
Abstract
The invention discloses a method for preparing gasoline by coupling synthesis gas with naphtha. The method can obviously improve the octane number of the gasoline.
Description
Technical Field
The invention relates to a method for preparing gasoline by coupling synthesis gas with naphtha, in particular to a method for preparing high-octane gasoline by coupling synthesis gas with naphtha.
Background
With the development of society and the increase of economic level, the demand for clean liquid fuels has also increased year by year. For the current situation of the shortage of petroleum resources in China, the technical route for converting the synthetic gas into the liquid fuel has important economic significance and strategic significance. China is rich in coal resources, and synthesis gas (CO and H) is obtained by gasifying coal2) The product obtained by the synthesis gas through the Fischer-Tropsch synthesis route follows Anderson-Schulz-Flory (ASF) distribution, the carbon number distribution is wide, the selectivity of gasoline fraction and diesel oil fraction is not high, and the application of the product has great limitation. The synthesis gas is reacted with a catalyst to obtain methanolThe dimethyl ether is prepared by dehydration, then the gasoline is prepared by the dimethyl ether, and the technical route of preparing the gasoline by two-stage reaction of the synthesis gas has higher cost. The technology for directly preparing gasoline by one-stage reaction of synthesis gas can greatly simplify the process flow, reduce the investment and improve the reaction efficiency of raw materials, and has great research significance and application prospect.
Patent CN200710061506.3 discloses a process for co-producing aromatic hydrocarbon by synthesizing gasoline with synthetic gas, which comprises mixing methanol synthesis and methanol dehydration catalyst, loading into a slurry bed reactor, loading ZSM-5 catalyst into a fixed bed reactor, and introducing diluted hydrogen (H) under normal pressure2/N2) Carrying out temperature programmed reduction on the catalyst in the slurry bed, preheating the fixed bed catalyst by the reduction tail gas, and introducing H into the slurry bed after the catalyst in the slurry bed is reduced2CO 1-5:1, at 3.0-7.0MPa, reaction temperature in slurry bed: 260 ℃ to 300 ℃, gas space velocity: 30000h-1-120000h-1Reaction, the reaction product enters a fixed bed with equal pressure, the reaction temperature of the fixed bed is 300-400 ℃, and the gas space velocity is 10000h-1-40000 h-1The synthesis reaction is carried out under the conditions of (1).
Patent CN201710407761.2 discloses a method for preparing liquid fuel and co-producing low-carbon olefins by directly converting catalyst and synthesis gas. The synthesis gas is used as a reaction raw material, and the reaction is carried out on a fixed bed or a moving bed, wherein the catalyst contains a component A and a component B, the component A is an active metal oxide, and the component B is a molecular sieve with a CDO structure; the mass ratio of the catalyst A to the catalyst B is 0.1-20. The pressure of the synthesis gas is 0.1-10Mpa, the reaction temperature is 300--1。
It is known that the octane number of gasoline is one of the important indexes for measuring the quality of gasoline performance, however, the octane number of the gasoline fraction synthesized by the above method is not high generally.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides a method for preparing gasoline by coupling synthesis gas with naphtha, which can obviously improve the octane number of the naphtha.
A method for preparing gasoline by coupling synthesis gas with naphtha comprises the steps of enabling the synthesis gas to enter a first reaction zone to carry out methanol synthesis reaction, enabling an effluent of the first reaction zone and naphtha to be mixed and then enter a second reaction zone to carry out aromatization reaction, and separating the effluent of the second reaction zone to obtain a gasoline product.
In the above method, the reaction conditions of the methanol synthesis reaction are as follows: the reaction temperature is 300-700 ℃, and preferably 200-400 ℃; the reaction pressure is 0.1-5Mpa, preferably 1-3 Mpa; synthetic gas integral volume space velocity 5000--1Preferably 10000--1。
In the method, the catalyst used in the methanol synthesis reaction is a Cu-based catalyst for preparing methanol from synthesis gas, the catalyst is a supported catalyst, the carrier is one or more of silicon dioxide, activated carbon, alumina, amorphous silica-alumina, titanium oxide, a Y molecular sieve and an A-type molecular sieve, preferably alumina, the catalyst can contain an auxiliary agent, and the auxiliary agent is one or more of K, Li, Na, Rh, Zn, B, Zr and oxides thereof, preferably Zn; based on the weight of the final catalyst, Cu is 20-70wt%, preferably 30-50 wt%, calculated by oxide, auxiliary Zn is 10-50 wt%, preferably 20-30 wt%, and the balance is carrier.
In the above method, the reaction conditions of the aromatization reaction are as follows: the reaction temperature is 300-600 ℃, preferably 300-450 ℃; the reaction pressure is 0.1-5Mpa, preferably 0.2-0.5 Mpa; the space velocity of the feeding of the naphtha liquid is 0.1 to 10h-1Preferably 0.5 to 1h-1。
In the method, the catalyst used for aromatization contains a ZSM-5 molecular sieve, the content of the ZSM-5 molecular sieve in the catalyst is 30% -100%, preferably 40% -90%, further preferably 50% -80%, further preferably 60% -70%, the catalyst optionally further contains one or more of molecular sieves such as SAPO-11, SAPO-34, ZSM-11, Silicalite-2, ZSM-35, Silicalite-1, TS-1, ZSM-12, ZSM-22 and the like, preferably contains one or more of SAPO-11, ZSM-12 and ZSM-35, the content of the optional molecular sieve in the catalyst is 0.1 to 40% by weight, preferably 1 to 30% by weight, and more preferably 5 to 20% by weight; and/or optionally contains one or more elements of IIIA, IVA, IIA, IVB, VIIIB, VIA and VA, and the content of the elements in the catalyst is 0.1-20 percent, preferably 1-10 percent calculated by oxide; the element is preferably one or more of B, P, Al, Si, Mg, Zr and Ni; and/or optionally contains one or more elements in VIIA, wherein the content of the elements in the catalyst is 0.01-20%, preferably 0.1-15%, and further preferably 0.5-5% calculated by simple substances, and the elements are preferably F.
In the method, before entering the second reaction zone, the molar ratio of hydrogen to carbon monoxide is controlled to be 5-100, preferably 10-50, by adding part of hydrogen, and the volume content of hydrogen is 0.1-30%, preferably 5-10%, before entering the second reaction zone. The hydrogen and the carbon monoxide in the effluent of the first reaction zone improve the gas phase gas partial pressure, inhibit the generation of dry gas in aromatization reaction and improve the liquid yield of gasoline components, and in addition, the improvement of the hydrogen entering the second reaction zone can inhibit the generation of coke on the catalyst, greatly improve the reaction operation period and prolong the service life of the catalyst.
In some embodiments of the present invention, the proportion of acid content > 350 ℃ of the ZSM-5 containing molecular sieve catalyst used at 450 ℃ to the total acid content below is less than 15%, preferably less than 10%, more preferably less than 5%, even more preferably 0.5% to 5%, and specifically may be 1%, 2%, 3%, 4%, and the catalyst may be selected from commercially available products or prepared by a method comprising the steps of: (1) selecting or self-making an aromatization catalyst; (2) treating the aromatization catalyst of step (1) to make the acidic sites in the catalyst adsorb compounds containing basic sites; (3) and (3) carrying out selective desorption on the material in the step (2) to restore partial acid sites, and optionally drying and roasting to obtain the final aromatization catalyst.
Compared with the prior art, the method for preparing the gasoline by coupling the synthesis gas with the naphtha can obviously improve the liquid yield and the octane number of the gasoline.
Detailed Description
The action and effect of the method of the present invention will be specifically described below with reference to examples, but the following examples are not intended to limit the method of the present invention. In the present application, unless otherwise specified,% is mass percent, and if the catalyst composition does not satisfy 100%, the balance is binder alumina.
Example 1
The synthesis gas (H2/CO = 2) enters the first reaction zone to carry out methanol synthesis reaction under the following reaction conditions: the reaction temperature is 200 ℃, the reaction pressure is 1Mpa, and the synthesis gas feeding space velocity is 10000h-1The catalyst composition is as follows: the content of copper oxide is 30 percent, the content of zinc is 20 percent, the effluent of the first reaction zone and naphtha are mixed and then enter a second reaction zone for aromatization reaction, and the reaction conditions are as follows: the reaction temperature is 300 ℃, the reaction pressure is 0.2Mpa, and the feeding space velocity of the effluent of the first reaction zone is 5h-1The space velocity of naphtha feeding is 0.5h-1The catalyst composition is as follows: 60% of ZSM-5, 5% of SAPO-11, 1% of P2O5 and 0.5% of F, and separating the effluent of the second reaction zone to obtain a gasoline product, wherein the gasoline performance is shown in Table 1.
Example 2
The synthesis gas (H2/CO = 2) enters the first reaction zone to carry out methanol synthesis reaction under the following reaction conditions: the reaction temperature is 400 ℃, the reaction pressure is 3Mpa, and the synthetic gas feeding airspeed is 30000h-1The catalyst comprises the following components of 50% of copper oxide and 30% of zinc, and the effluent of the first reaction zone and naphtha are mixed and then enter the second reaction zone for aromatization reaction under the following reaction conditions: the reaction temperature is 450 ℃, the reaction pressure is 0.5Mpa, and the feeding space velocity of the effluent of the first reaction zone is 10h-1The space velocity of naphtha feeding is 1h-1The catalyst comprises the following components of 70% of ZSM-5, 20% of SAPO-11, 10% of P2O5 and 5% of F, and the effluent of the second reaction zone is separated to obtain a gasoline product, wherein the gasoline performance is shown in Table 1.
Example 3
The synthesis gas (H2/CO = 2) enters the first reaction zone to carry out methanol synthesis reaction under the following reaction conditions: the reaction temperature is 300 ℃, the reaction pressure is 2Mpa, and the synthetic gas feeding airspeed is 20000h-1The catalyst comprises the following components of 40% of copper oxide and 25% of zinc, and the effluent of the first reaction zone and naphtha are mixed and then enter the second reaction zone for aromatization reaction under the following reaction conditions: the reaction temperature is 400 ℃, the reaction pressure is 0.3Mpa, and the feeding space velocity of the effluent of the first reaction zone is 8h-1Naphtha of petroleumThe feeding airspeed is 0.7h-1The catalyst comprises 65% of ZSM-5, 15% of SAPO-11, 5% of P2O5 and 2% of F, and the effluent of the second reaction zone is separated to obtain a gasoline product, wherein the gasoline performance is shown in Table 1.
Example 4
The synthesis gas (H2/CO = 2) enters the first reaction zone to carry out methanol synthesis reaction under the following reaction conditions: the reaction temperature is 200 ℃, the reaction pressure is 1Mpa, and the synthesis gas feeding space velocity is 10000h-1The catalyst comprises the following components of 30 percent of copper oxide and 20 percent of zinc, and the components are controlled to be as follows before entering the second reaction zone: hydrogen/carbon monoxide =10, hydrogen content 5%; the effluent of the first reaction zone and naphtha are mixed and then enter a second reaction zone for aromatization reaction, wherein the reaction conditions are as follows: the reaction temperature is 300 ℃, the reaction pressure is 0.2Mpa, and the feeding space velocity of the effluent of the first reaction zone is 5h-1The space velocity of naphtha feeding is 0.5h-1The catalyst comprises 60% of ZSM-5, 5% of SAPO-11, 1% of P2O5 and 0.5% of F, and the effluent of the second reaction zone is separated to obtain a gasoline product, wherein the gasoline performance is shown in Table 1 (the outstanding octane number is high, the liquid yield is high, and the running period is long).
Example 5
The synthesis gas (H2/CO = 2) enters the first reaction zone to carry out methanol synthesis reaction under the following reaction conditions: the reaction temperature is 200 ℃, the reaction pressure is 1Mpa, and the synthesis gas feeding space velocity is 10000h-1The catalyst comprises the following components of 30% of copper oxide and 20% of zinc, and the composition of the effluent is controlled as the following components of hydrogen/carbon monoxide =50 and 10% of hydrogen; the effluent of the first reaction zone and naphtha are mixed and then enter a second reaction zone for aromatization reaction, wherein the reaction conditions are as follows: the reaction temperature is 300 ℃, the reaction pressure is 0.2Mpa, and the feeding space velocity of the effluent of the first reaction zone is 5h-1The space velocity of naphtha feeding is 0.5h-1The catalyst comprises 60% of ZSM-5, 5% of SAPO-11, 1% of P2O5 and 0.5% of F, and the effluent of the second reaction zone is separated to obtain a gasoline product, wherein the gasoline performance is shown in Table 1.
Example 6
The synthesis gas (H2/CO = 2) enters the first reaction zone to carry out methanol synthesis reaction under the following reaction conditions: reaction ofThe temperature is 200 ℃, the reaction pressure is 1Mpa, and the synthetic gas feeding space velocity is 10000h-1The catalyst comprises the following components of 30% of copper oxide and 20% of zinc, and the composition of the effluent is controlled to be hydrogen/carbon monoxide =10 and the hydrogen content is 5%; the effluent of the first reaction zone and naphtha are mixed and then enter a second reaction zone for aromatization reaction, the reaction conditions are that the reaction temperature is 300 ℃, the reaction pressure is 0.2Mpa, and the feeding airspeed of the effluent of the first reaction zone is 5h-1The space velocity of naphtha feeding is 0.5h-1The catalyst comprises 60 percent of ZSM-5, 5 percent of SAPO-11, 1 percent of P2O5 and 0.5 percent of F, the proportion of the acid content of the aromatization catalyst of the second reaction zone at the temperature of more than 350 ℃ to the total acid content below 450 ℃ is controlled to be 1 percent, and the effluent of the second reaction zone is separated to obtain a gasoline product, wherein the gasoline performance is shown in Table 1.
Example 7
The synthesis gas (H2/CO = 2) enters the first reaction zone to carry out methanol synthesis reaction under the following reaction conditions: the reaction temperature is 200 ℃, the reaction pressure is 1Mpa, and the synthesis gas feeding space velocity is 10000h-1The catalyst comprises the following components of 30% of copper oxide and 20% of zinc, and the composition of the effluent is controlled to be hydrogen/carbon monoxide =10 and the hydrogen content is 5%; the effluent of the first reaction zone and naphtha are mixed and then enter a second reaction zone for aromatization reaction, the reaction conditions are that the reaction temperature is 300 ℃, the reaction pressure is 0.2Mpa, and the feeding airspeed of the effluent of the first reaction zone is 5h-1The space velocity of naphtha feeding is 0.5h-1The catalyst comprises 60 percent of ZSM-5, 5 percent of SAPO-11, 1 percent of P2O5 and 0.5 percent of F, the proportion of the acid content of the aromatization catalyst of the second reaction zone at the temperature of more than 350 ℃ to the total acid content below 450 ℃ is controlled to be 4 percent, and the effluent of the second reaction zone is separated to obtain a gasoline product, wherein the gasoline performance is shown in Table 1.
Comparative example 1
Compared with example 1, naphtha was not introduced, and other process parameters and catalyst composition 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 described in example 1.
TABLE 1 Properties of the products
Claims (11)
1. A method for preparing gasoline by coupling synthesis gas with naphtha is characterized in that: the synthesis gas enters a first reaction zone to carry out methanol synthesis reaction, the effluent of the first reaction zone and naphtha are mixed and then enter a second reaction zone to carry out aromatization reaction, and the effluent of the second reaction zone is separated to obtain a gasoline product.
2. The method of claim 1, wherein: the reaction conditions for the methanol synthesis reaction are as follows: the reaction temperature is 300 ℃ and 700 ℃; the reaction pressure is 0.1-5 Mpa; synthetic gas integral volume space velocity 5000--1。
3. The method of claim 2, wherein: the reaction conditions for the methanol synthesis reaction are as follows: the reaction temperature is 200-400 ℃; the reaction pressure is 1-3 Mpa; the integral volume airspeed of the synthetic gas is 10000-30000h-1。
4. The method of claim 1, wherein: the reaction conditions of the aromatization reaction are as follows: the reaction temperature is 300-600 ℃; the reaction pressure is 0.1-5 Mpa; the space velocity of the feeding of the naphtha liquid is 0.1 to 10h-1。
5. The method of claim 4, wherein: the reaction conditions of the aromatization reaction are as follows: the reaction temperature is 300-450 ℃; the reaction pressure is 0.2-0.5 Mpa; the space velocity of the feeding of the naphtha liquid is 0.5 to 1h-1。
6. The method of claim 1, wherein: before entering the second reaction zone, the mol ratio of hydrogen and carbon monoxide after the effluent of the first reaction zone is mixed with naphtha is controlled to be 5-100, and the volume content of hydrogen is 0.1-30%.
7. The method of claim 6, wherein: before entering the second reaction zone, the mol ratio of hydrogen and carbon monoxide after the effluent of the first reaction zone is mixed with naphtha is controlled to be 10-50, and the volume content of hydrogen is 5-10%.
8. The method of claim 1, wherein: the catalyst used in the methanol synthesis reaction is a Cu-based catalyst, the catalyst is a supported catalyst, and the carrier is one or more of silicon dioxide, activated carbon, alumina, amorphous silica-alumina, titanium oxide, a Y molecular sieve and an A molecular sieve.
9. The method of claim 1, wherein: the catalyst contains an auxiliary agent, wherein the auxiliary agent is one or more of K, Li, Na, Rh, Zn, B, Zr and oxides thereof, and Zn is preferred.
10. The method of claim 1, wherein: the catalyst used for the aromatization reaction contains a ZSM-5 molecular sieve, and the content of the ZSM-5 molecular sieve in the catalyst is 30-100 percent, preferably 40-90 percent, further preferably 50-80 percent, and further preferably 60-70 percent based on the weight of the final catalyst.
11. The method of claim 10, wherein: the proportion of the acid content of the ZSM-5 molecular sieve-containing catalyst at the temperature of more than 350 ℃ in the total acid content below 450 ℃ is less than 15 percent, preferably less than 10 percent, more preferably less than 5 percent, and even more preferably 0.5 to 5 percent.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4048250A (en) * | 1975-04-08 | 1977-09-13 | Mobil Oil Corporation | Conversion of natural gas to gasoline and LPG |
| CN102686540A (en) * | 2009-11-17 | 2012-09-19 | 开姆尼斯化工有限公司 | Method for generating hydrocarbons, in particular gasoline, from synthesis gas |
| CN104910957A (en) * | 2015-06-09 | 2015-09-16 | 天津市福生染料厂 | Process for preparing high-octane-rating high-cleaning gasoline based on naphtha and methanol as raw materials |
| CN104941695A (en) * | 2015-06-08 | 2015-09-30 | 清华大学 | Nano ZSM-5 molecular sieve based catalyst and preparation and use methods |
| CN107974297A (en) * | 2016-10-21 | 2018-05-01 | 中国石油化工股份有限公司 | A kind of vapour oil treatment process |
| CN111770978A (en) * | 2018-02-16 | 2020-10-13 | 开姆尼茨化工工程有限公司 | Method and device for producing synthetic gasoline |
-
2020
- 2020-10-19 CN CN202011115274.7A patent/CN114437772B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4048250A (en) * | 1975-04-08 | 1977-09-13 | Mobil Oil Corporation | Conversion of natural gas to gasoline and LPG |
| CN102686540A (en) * | 2009-11-17 | 2012-09-19 | 开姆尼斯化工有限公司 | Method for generating hydrocarbons, in particular gasoline, from synthesis gas |
| CN104941695A (en) * | 2015-06-08 | 2015-09-30 | 清华大学 | Nano ZSM-5 molecular sieve based catalyst and preparation and use methods |
| CN104910957A (en) * | 2015-06-09 | 2015-09-16 | 天津市福生染料厂 | Process for preparing high-octane-rating high-cleaning gasoline based on naphtha and methanol as raw materials |
| CN107974297A (en) * | 2016-10-21 | 2018-05-01 | 中国石油化工股份有限公司 | A kind of vapour oil treatment process |
| CN111770978A (en) * | 2018-02-16 | 2020-10-13 | 开姆尼茨化工工程有限公司 | Method and device for producing synthetic gasoline |
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