CN102690677A - Method for producing high-octane number clean gasoline by combining alkane aromatization and olefin aromatization of liquefied gas - Google Patents
Method for producing high-octane number clean gasoline by combining alkane aromatization and olefin aromatization of liquefied gas Download PDFInfo
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- CN102690677A CN102690677A CN2012101867467A CN201210186746A CN102690677A CN 102690677 A CN102690677 A CN 102690677A CN 2012101867467 A CN2012101867467 A CN 2012101867467A CN 201210186746 A CN201210186746 A CN 201210186746A CN 102690677 A CN102690677 A CN 102690677A
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Abstract
The invention discloses a method for producing high-octane number clean gasoline by combining alkane aromatization and olefin aromatization of liquefied gas. The method is characterized in that the upper section of a reactor is filled with an alkane aromatization catalyst, and the lower section of the reactor is filled with an olefin aromatization catalyst. After the liquefied gas enters the reactor, olefin in the liquefied gas is subjected to superposition, cyclization and aromatization reaction under the action of the olefin aromatization catalyst to form aromatic oil, and alkane in the liquefied gas is subjected to dehydrogenation, cracking, superposition, cyclization, aromatization and other reaction under the action of the alkane aromatization catalyst to form aromatic oil. The alkane aromatization reaction is combined with the traditional alkane aromatization, the requirement for olefin content in a raw material in the traditional alkane aromatization process is reduced, the flexibility of the aromatization process is improved and the raw material conversion rate and gasoline yield are greatly improved.
Description
Technical field
The present invention relates to the method for a kind of liquefied gas alkane aromatization and alkene aromizing combinations produce high-octane rating clean gasoline.Specifically a kind of alkane in the liquefied gas and alkene all are converted into the method for the clean gasoline of high added value, the gasoline octane rating that reaction generates is higher, and sulphur content is very low, is ideal high-octane rating clean gasoline blend component.
Background technology
At present oil is as Nonrenewable resources worsening shortages, and world's petrol and diesel oil demand keeps sustainable growth situation, has therefore caused the high position operation of oil price inevitably.According to Purvin&Gertz whole world oil market analysis report, China's gasoline demand amount expectation will increase to 12,500 ten thousand tons/year in 2016 from 8,700 ten thousand tons/year in 2011, and annual growth will reach 7.7%.How maximally utilising limited petroleum resources produces the petrol and diesel oil product that supply falls short of demand and becomes oil refining enterprise already and be badly in need of the difficult problem that solves.
Simultaneously, in order to satisfy the requirement of energy-saving and emission-reduction, China's petrol and diesel oil quality standard is improving constantly.From on June 1st, 2012 Beijing come into effect five-stage motor spirit and diesel oil standard, i.e. " capital five standards ", this be China first be equivalent to the provincial standard of Europe five standards basically.The sulphur content index of capital five standards will drop to 10ppm from 50ppm, and will be in full accord with Europe five standards, and other indexs are also basically with reference to European Union's standard formulation.But; 80% blend component is the catalytically cracked gasoline of high olefin content in China's unleaded gasoline for vehicle at present; Olefin(e) centent is up to 35%～55%; And the maximum aromaticity content (aromatic hydrocarbons+alkene) of Europe five standards is merely 35%, and the clean gasoline component output that octane value is higher, olefin(e) centent is low is very limited.Therefore, seeking development new technologies, to produce the high-octane rating clean gasoline imperative.
On the other hand,, the appreciable liquefied gas of quantity is arranged in the world wide, wherein contain abundant C4 olefin feedstock along with the continuous development of petroleum refining industry.Present most of refinery is with the sale that acts as a fuel of this part liquefied gas, and this has obviously caused the huge waste of resource.And the liquefied gas technique for preparing gasoline can effectively utilize this part low value-added liquefied gas, produces the high-octane rating clean gasoline that supply falls short of demand on the market, can improve the economic benefit of refinery largely.
A kind of method of preparing gasoline from liquefied gas through aromatization is disclosed among the CN201010201829X.This method is removed sectional feeding behind the impurity such as methyl alcohol, dme with liquid stock gasification washing; The back gets into from the fixed-bed reactor top about main feeding preheating to 300 ℃; Several roads cold feed gets into reactor drum between each filling batch in addition, and it is constant to keep temperature of reactor to take away reaction heat.The temperature of reaction of this method is 280～410 ℃, and yield of gasoline is up to 45%, and RON is greater than 93, and olefin(e) centent is less than 10%.Just can reach the ideal product yield but the raw material of this method need carry out a series of complicated pretreatment, and this patent is not considered the associativity of technology of aromatization yet.
A kind of liquefied gas cracking system propylene of butylene and process method of ethene of containing disclosed among the CN2011104484700.This method is at reactor drum epimere filling polymerization catalyst, and catalyst for cracking is loaded in the reactor drum lower end, and the liquid stock gasification gets into from reactor top, and building-up reactions and scission reaction successively take place under the effect of two kinds of catalyzer.This technology is main products with the propylene, and propene yield can reach 25%, and yield of gasoline is more than 18%, and gasoline octane rating is high, and RON is greater than 97, and sulphur content is very low in a small amount of diesel oil that gasoline and fractionation obtain, and is the fine clean fuel oil.
Announced a kind of method of C4 component two-stage polymerization system gasoline among the US4544791.The raw material of this method is a butylene of removing divinyl and other alkane, mainly comprises iso-butylene, 1-butylene and 2-butylene.80% iso-butylene and 45% 1-butylene, 2-butylene polymerization obtain dimer and tripolymer in the gasoline fraction scope in the first step polyreaction; Product is through separation column; Obtain gasoline at the bottom of the tower; Cat head is unreacted 1-butylene, 2-butylene and iso-butylene, and the logistics of cat head continues to take place the second step polyreaction, and 75% 1-butylene and 55% 2-butylene polymerization obtain dimer and tripolymer in the gasoline fraction scope.40 ℃ of polyreaction temperature ins; 250 ℃ of temperature outs, reaction pressure 0.1～10MPa, volume space velocity 0.05～5h-1; This method yield of gasoline is up to 84%; Gasoline octane rating is up to 99.5, and this possibly be because do not contain divinyl in the used raw material of this technology, and iso-butylene, 1-butylene and 2-butylene content sum are greater than 91%.
Announced the method for a kind of C4 component priority polymerization reaction take place and alkylated reaction system gasoline among the US4367356.This method is raw materials used to be the mixture of butylene and butane, at first raw material is divided into and forms identical two strands, and one raw material is polymerization reaction take place under the effect of catalyzer; Comprise Trimethylmethane, iso-butylene, n-butene and C8 hydro carbons in the reacted logistics; Reclaim the C8 component, Trimethylmethane, iso-butylene and n-butene and second burst of raw materials mix with remaining get in another reactor drum; Butylene and Trimethylmethane generation alkylated reaction generate the C8 hydro carbons.Two bursts of C8 hydro carbons mixing fractionation are obtained gasoline.120～260 ℃ of this technology polymeric reaction temperatures, reaction pressure 0.1～8.3MPa, 10～60 ℃ of alkylated reaction temperature, reaction pressure 0.1～3.5MPa.But this method lacks the description of technological effect and detailed specific embodiment etc.
The invention provides the method for a kind of liquefied gas alkane aromatization and alkene aromizing combinations produce high-octane rating clean gasoline; This method adopts two sections or multistage beds; That alkene in the liquid stock gasification takes place under the effect of reactor drum hypomere alkene aromatized catalyst is superimposed, cyclisation and aromatization generate aromatic hydrocarbon oil; Reactions such as dehydrogenation, cracking, superimposed, cyclisation and aromizing take place in the alkane in the liquefied gas under the effect of epimere alkane aromatization catalyst, generate aromatic hydrocarbon oil.Compare with other liquefied gas system process of gasoline; This technology does not have strict requirement to the olefin(e) centent in the liquid stock gasification; Alkane in the liquid stock gasification and alkene can both be converted into title product gasoline; This point has been improved the handiness of technology of aromatization to a great extent, has improved feed stock conversion and yield of gasoline greatly.
One aspect of the present invention can effectively be utilized the lower liquefied gas raw material of superfluous relatively added value, can not contained the clean gasoline product that supply falls short of demand on motor liquified gas and the market of alkene on the other hand again, has broad application prospects.
Summary of the invention
The method that the purpose of this invention is to provide a kind of liquefied gas alkane aromatization and alkene aromizing combinations produce high-octane rating clean gasoline; This method combines alkane aromatization reaction and traditional alkene aromatization; Reduced of the requirement of traditional alkene technology of aromatization to olefin(e) centent in the raw material; Improve the handiness of technology of aromatization, improved feed stock conversion and yield of gasoline greatly.
The present invention can not only effectively utilize more low value-added liquefied gas to produce the gasoline of high added value; And do not contain alkene in the reacted poor alkene liquefied gas; Be the fine motor liquified gas, this technology can improve the economic worth of liquefied gas effectively, improves the economic benefit of oil refining enterprise.
For realizing above-mentioned purpose, the present invention includes following steps:
(1) the liquid stock gasification gets into reactor drum between two sections filling batch, after the reaction product of the effusive alkane aromatization of reactor drum epimere is mixed, superimposed, cyclisation and aromatization takes place under the effect of reactor drum hypomere alkene aromatized catalyst;
(2) the aromizing product gets into separation system after the heat exchange cooling, reclaims the gasoline that reaction generates;
(3) the poor alkene liquefied gas that comes out of separation system gets into from reactor top through heat exchange and/or heating back, reactions such as generation dehydrogenation under the effect of alkane aromatization catalyst, cracking, superimposed, cyclisation and aromizing;
(4) reaction product of alkane aromatization part is mixed back entering reactor drum hypomere with the liquid stock gasification, and reaction generates title product gasoline under the effect of alkene aromatized catalyst.
The present invention is with two reactions; Be reactions such as the dehydrogenation, cracking of alkane in the superimposed and aromatization of alkene in the liquid stock gasification, the poor alkene liquefied gas, superimposed, cyclisation and aromizing; In same reactor drum, carry out; Make full use of the heat that heat that the alkane cracking reaction product takes out of and alkene aromatization generate, when improving liquid stock gasification transformation efficiency, can obtain higher aromatic hydrocarbon oil yield.Detailed process is: under the effect of the alkane aromatization catalyst that the reactor drum epimere loads; The reaction that alkane cracking generates propylene and ethylene at first takes place in poor alkene liquefied gas; This reaction is thermo-negative reaction; The effusive hydrocarbon mixture temperature in reaction back is up to 500～650 ℃, and the liquid stock gasification arrives 110～350 ℃ of gasification temperatures through heat exchange; Superimposed, the aromatization that are used for liquid stock gasification alkene at reactor drum hypomere filling alkene aromatization catalyzer; This reaction is thermopositive reaction; The heat that utilizes the effusive high temperature hydrocarbon mixture of this part reaction heat and epimere alkane aromatization catalyst bed to take out of can directly reach alkene aromatization optimal temperature, the aromatic hydrocarbon oil productive rate that the present invention has got back higher in save energy.
The liquefied gas that the present invention mentioned mainly is meant the liquefied gas that is produced in refinery, ethylene plant, the coal processing, and wherein the liquefied gas of refinery is meant catalytic cracking liquefied gas, coking liquefied gas.Butene component comprises n-butene, anti-butylene, maleic, iso-butylene, also contains propylene, the propane of normal butane, Trimethylmethane and minute quantity in addition in the liquefied gas.
The beds of reactor drum of the present invention can be divided into more than two sections or two sections, reactor drum epimere filling alkane aromatization catalyst, reactor drum hypomere filling alkene aromatized catalyst.Because the alkene aromatized catalyst has unique selectivity and activity; Only carry out superimposed, the aromatization of alkene at the reactor drum hypomere; Simultaneously because alkane aromatization catalyst also has unique selectivity and activity, only carry out reactions such as the dehydrogenation, cracking of alkane, superimposed, cyclisation and aromizing at the reactor drum epimere.
Among the present invention, the liquid stock gasification mixes the back and gets into reactor drum with the alkane aromatization reaction product.Reactor drum hypomere alkene aromatization condition is: the temperature of reaction of reactor drum lower section catalyst bed is 300～500 ℃, and weight space velocity is 0.2～3.0h
-1, reaction pressure is 0.4～1.8MPa; Poor alkene liquefied gas that separation system is come out and the effusive gas-oil mixture heat exchange of reactor bottom are to 110～350 ℃ of preheating temperatures; Get into reactor drum from reactor head; Reactions such as dehydrogenation, cracking, superimposed, cyclisation and aromizing take place under the effect of reactor drum epimere alkane aromatization catalyst; The reaction conditions of reactor drum epimere alkane aromatization part is: reactor drum epimere catalyst bed reaction temperature is 400～550 ℃, and weight space velocity is 0.3～4.0h
-1Reaction pressure is 0.4～1.8MPa.
The gas-oil mixture that reaction generates flows out from reactor bottom; The poor alkene liquefied gas heat exchange of coming out through interchanger and separation system; Get into that condensing surface cools after the supercharging of overdraft machine, the poor alkene dry gas of gas phase gets into the absorption tower with liquefied gas, liquid phase entering desorption tower; Dry gas ejects from the absorption tower, removes the gas pipe network; Liquefied gas gasoline etc. get into stabilizer tower and separation column, isolate the poor alkene liquefied gas, stop bracket gasoline and the heavy aromatics oil that contain propane.The poor alkene liquefied gas that contains propane also can get into depropanizing tower, further separates into thick propane and cymogene, and butane carries out freshening, gets into the alkane aromatization catalyst bed.
When adopting higher reaction pressure, like reaction pressure greater than 1.2MPa, the material that reactor drum comes out, after the heat exchange cooling, the separation system of directly going to the back.
Eject the cymogene that contains the poor alkene liquefied gas of propane and/or come out at the bottom of the depropanizing tower that comes from stabilizer tower; Be divided into two strands; One is drawn directly as motor liquified gas, and a stock-traders' know-how interchanger gets into from reactor head after being heated to 110～350 ℃ of preheating temperatures; Reactions such as dehydrogenation, cracking, superimposed, cyclisation and aromizing take place under the effect of alkane aromatization catalyst, and its reaction product gets into the alkene aromatization part of reactor drum hypomere after heat exchange.
Alkene aromatized catalyst and alkane aromatization catalyst that the present invention is used are metal-modified sieve catalyst, and catalyzer comprises 0.1～10% modified metal-oxide, 40～90% molecular sieves, 10～50% aluminum oxide.In the preferred HZSM-5 of used molecular sieve, HZSM-11, mordenite, the USY molecular sieve a kind of, two or more, more preferably HZSM-5, mordenite or the mixture of the two.As the carrier of metal, metal adopts pickling process to be downloaded on the catalyzer jointly for molecular sieve and alumina binder.The difference of alkene aromatized catalyst and alkane aromatization catalyst component mainly is the different of modified metal-oxide.The catalyzer that is used for the alkene aromatization at the reactor drum hypomere is the catalyzer that our company develops voluntarily; See patent ZL200810084129X; MOX wherein is a kind of in the oxide compound of Ni, Zn, Cr, La, Ce, Ti, P or their mixture, preferred Ni, Zn, P, the oxide compound of La or the mixture of the two.The MOX that is used for the catalyzer of alkane aromatization reaction at the reactor drum epimere is oxide compound a kind of of Zr, Cr, La, Ce, Ti or their mixture, preferred Zr, Cr, the oxide compound of La or the mixture of the two.
The forming method of catalyzer is that those skilled in the art know among the present invention, like extrusion, compressing tablet, round as a ball a, ball.Solids such as molecular sieve, white lake, sesbania powder are mixed, add suitable quantity of water and acid (hydrochloric acid, nitric acid or acetic acid), extruding is mediated, and last extrusion drying fragments into bar shaped, or the round as a ball globulate of extrusion; Maybe all raw materials mix are processed colloid, in deep fat or the bath of oily ammonia, drip the ball globulate.Catalyzer after the moulding is dry under the condition of room temperature～150 ℃; The method that dry back is flooded with metal soluble salt (generally being nitrate salt) with metal deposition to catalyzer; Then under 400～700 ℃ temperature; Roasting 1～24h in air and/or the vapor atmosphere promptly obtains catalyzer of the present invention.
The present invention has following effect:
(1) compare with traditional liquefied gas system process of gasoline, alkene in the liquefied gas and alkane all can be converted into title product gasoline, so the liquefied gas transformation efficiency is high, and yield of gasoline is high.
(2) be raw material with carbon 4 liquid gas behind the ether of olefin(e) centent 40%, yield of gasoline of the present invention can reach 60%;
(3) gasoline octane rating is high, and RON is greater than 93, and sulphur content is very low in gasoline and a small amount of diesel oil, is the fine clean fuel oil;
(4) do not contain alkene in the poor alkene liquefied gas that separation system is come out, can be directly as the fine motor liquified gas;
Description of drawings
Fig. 1 is the inventive method process flow diagram.
The technical process of present technique shown in Figure 1 is: the liquid stock gasification gets in the reactor drum with after the alkane aromatization reaction product mixes; Superimposed, aromatization takes place under the effect of reactor drum hypomere alkene aromatized catalyst; The aromizing product flows out from reactor bottom; After the heat exchange cooling, get into separation system, reclaim the gasoline that reaction generates; The poor alkene liquefied gas that separation system is come out is partly drawn as motor liquified gas; At the bottom of remainder and the reactor drum heat exchange of effusive aromizing product and/or be heated to certain temperature after get into from reactor top; Reactions such as dehydrogenation, cracking, superimposed, cyclisation and aromizing take place under the effect of alkane aromatization catalyst, generate title product gasoline.
Embodiment
Through instance the present invention is described below, but the present invention is not limited to this.
Raw material specification
(1) the liquid stock gasification is a carbon 4 liquid gas behind the ether of the Yanshan Mountain, and its composition is seen table 1.
(2) butane of freshening is that the configuration of butane composition forms in the analoging industrial device, and wherein Trimethylmethane content 73.6%, normal butane content 26.4%.
(3) alkane aromatization catalyst A, model PTL-1, outward appearance is the strip in 2.1mm * 3.2mm butterfly cross section, long 4～10mm.This model catalyzer is that Huiersanji Green Chemical Science and Technology Co., Ltd., Beijing produces, and wherein contains 56.8%ZSM-5,1.5%P
2O
5, 5.6%La
2O
3, 0.46%Cr
2O
3And the Al of surplus
2O
3The ZSM-5 molecular sieve is synthetic for the in-situ crystallization method, and silica alumina ratio is 45.
(4) alkene aromatized catalyst B, model LTG-3, outward appearance is the strip of Φ 1.8mm, long 3～10mm.This model catalyzer is that Huiersanji Green Chemical Science and Technology Co., Ltd., Beijing produces, and wherein contains 78.2%ZSM-5,2.2%NiO, 0.3%La
2O
3And the Al of surplus
2O
3The silica alumina ratio of ZSM-5 molecular sieve is 38.
Embodiment 1
The technological effect of this instance explanation liquefied gas alkane aromatization and alkene aromizing combinations produce high-octane rating clean gasoline.
In this instance, carbon 4 liquid gas is squeezed into the fixed-bed reactor with volume pump between beds behind the raw material ether, and raw material butane (Trimethylmethane content 73.6%, normal butane content 26.4%) is squeezed into preheater, got into reactor head with volume pump.The gas-oil mixture that reaction generates by the variable valve control pressure, through condensation and gas-liquid separator, is told the liquid that reaction generates through heat exchange, and liquid obtains gasoline and calculated yield through the distillation cutting.
Testing apparatus adopts the 300ml fixed-bed reactor, reactor inside diameter 40mm, and reactor drum is controlled to simulate industrial adiabatic reaction by electrically heated.Reactor drum epimere filling alkane aromatization catalyst A 120g, hypomere filling alkene aromatized catalyst B 80g.Raw materials used is carbon 4 liquid gas behind the ether of the Yanshan Mountain, and its composition is seen table 1, and the butane flow is 60g/h, and carbon four flows are 40g/h behind the ether.510 ℃ of epimere bed medial temperatures, 393 ℃ of hypomere bed medial temperatures, the pressure 1.1MPa (gauge pressure) of whole reactor.Successive reaction 7 days is got two secondary data (quality of liquid and compositional analysis) every day.Table 2 is average datas of 7 days, liquid (C5+ gasoline) yield 59.7% wherein, and diesel yield 1.6%, gasoline octane rating RON reaches 95.4.
The composition of table 1 liquid stock gasification
| Component | Mass percent, W% |
| Ethane | 0.25 |
| Ethene | 0.36 |
| Propane | 2.10 |
| Propylene | 0.82 |
| Normal butane | 12.14 |
| Trimethylmethane | 38.55 |
| N-butene | 16.57 |
| Iso-butylene | 1.95 |
| Maleic | 15.26 |
| Anti-butylene | 12.00 |
| Amount to | 100 |
The test conditions of table 2 instance 1 and yield
| Alkane aromatization catalyst | PTL-1 |
| The alkene aromatized catalyst | LTG-3 |
| The alkane aromatization average reaction temperature, ℃ | 510 |
| Alkene aromizing average reaction temperature, ℃ | 393 |
| The alkane aromatization reaction air speed, 1/h | 0.5 |
| Alkene aromatization air speed, 1/h | 1.0 |
| Total reaction pressure, MPa | 1.1 |
| The C5+ yield of gasoline | 59.7％ |
| Diesel yield | 1.6％ |
| The gasoline main character | |
| Density (20 ℃), g.cm -3 | 0.7266 |
| Octane value RON | 95.4 |
| MON | 85.7 |
| Sulphur content, μ gg -1 | 23 |
| Alkane content. ω % | 31.3 |
| Olefin(e) centent, ω % | 17.8 |
| Aromaticity content, ω % | 50.9 |
| Boiling range, ℃ | |
| Over point | 38 |
| 10％ | 79 |
| 50％ | 135 |
| 90％ | 175 |
Claims (6)
1. the method for liquefied gas alkane aromatization and alkene aromizing combinations produce high-octane rating clean gasoline may further comprise the steps:
(1) the liquid stock gasification gets into reactor drum between two sections filling batch, after the reaction product of the effusive alkane aromatization of reactor drum epimere is mixed, superimposed, cyclisation and aromatization takes place under the effect of reactor drum hypomere alkene aromatized catalyst;
(2) the aromizing product gets into separation system after the heat exchange cooling, reclaims the gasoline that reaction generates;
(3) the poor alkene liquefied gas that comes out of separation system gets into from reactor top through heat exchange and/or heating back, reactions such as generation dehydrogenation under the effect of alkane aromatization catalyst, cracking, superimposed, cyclisation and aromizing;
(4) reaction product of alkane aromatization part is mixed back entering reactor drum hypomere with the liquid stock gasification, and reaction generates title product gasoline under the effect of alkene aromatized catalyst.
2. method according to claim 1 is characterized in that liquefied gas is meant the liquefied gas that is produced in refinery, ethylene plant, the coal processing.
3. method according to claim 1 is characterized in that the beds of said reactor drum can be divided into more than two sections or two sections, reactor drum epimere filling alkane aromatization catalyst, reactor drum hypomere filling alkene aromatized catalyst.
4. method according to claim 1; It is characterized in that two reactions; Be reactions such as the dehydrogenation, cracking of alkane in the superimposed and aromatization of alkene in the liquid stock gasification, the poor alkene liquefied gas, superimposed, cyclisation and aromizing; In same reactor drum, carry out, made full use of the heat that heat that the alkane cracking reaction product takes out of and alkene aromatization generate.
5. according to the method for claim 1, it is characterized in that the reaction conditions of reactor drum hypomere is in the step (1): 300～500 ℃ of reactor drum lower section catalyst bed temperature of reaction, weight space velocity 0.2～3.0h
-1, reaction pressure is 0.4～1.8MPa.
6. according to the method for claim 1, it is characterized in that the reaction conditions of reactor drum epimere is in the step (3): 400～550 ℃ of reactor drum epimere catalyst bed reaction temperature, weight space velocity 0.3～4.0h
-1, reaction pressure is 0.4～1.8MPa.
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| CN107523327A (en) * | 2017-09-15 | 2017-12-29 | 武汉凯顺石化科技有限公司 | The reuse means and method of C4 accessory substances obtained by a kind of gasoline production |
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| CN101333461A (en) * | 2008-03-25 | 2008-12-31 | 北京惠尔三吉绿色化学科技有限公司 | Method for producing cleaning fuel oil form petroleum cracking dry gas and C4 component |
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| CN107523327A (en) * | 2017-09-15 | 2017-12-29 | 武汉凯顺石化科技有限公司 | The reuse means and method of C4 accessory substances obtained by a kind of gasoline production |
| CN108459015A (en) * | 2018-05-04 | 2018-08-28 | 濮阳市盛源能源科技股份有限公司 | A kind of detection method for producing silicone content in four unstripped gas of carbon after the ether of isooctane |
| CN109321268A (en) * | 2018-11-15 | 2019-02-12 | 中国科学院山西煤炭化学研究所 | A kind of Fischer-Tropsch process exhaust prepares the method and device thereof of gasoline and aromatic hydrocarbons |
| CN112742309A (en) * | 2019-10-31 | 2021-05-04 | 中国石油化工股份有限公司 | Method for preparing high-octane gasoline |
| CN111170817A (en) * | 2020-01-17 | 2020-05-19 | 太原理工大学 | High-stability and high-selectivity catalytic reaction process for preparing aromatic hydrocarbon from methanol |
| CN111170817B (en) * | 2020-01-17 | 2022-09-23 | 太原理工大学 | High-stability and high-selectivity catalytic reaction process for preparing aromatic hydrocarbon from methanol |
| CN116371456A (en) * | 2023-06-02 | 2023-07-04 | 潍坊正轩稀土催化材料有限公司 | Liquefied gas aromatization catalyst and preparation method thereof |
| CN116371456B (en) * | 2023-06-02 | 2023-09-15 | 潍坊正轩稀土催化材料有限公司 | Liquefied gas aromatization catalyst and preparation method thereof |
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Application publication date: 20120926 |