CN1242027C - Process for modifying petrol by etherification and aromatization - Google Patents
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Abstract
The present invention relates to a process for modifying petrol by etherification and aromatization. Petrol is distilled to be divided into a light petrol component A and a heavy petrol component B, wherein the olefin and the alcohol of the light petrol component A are etherified; in addition, the heavy petrol component B is aromatized. Two products after reaction are mixed, and petrol with low olefin contents and high octane values is obtained.
Description
Technical field
The present invention relates to a kind of technology of reformulated gasoline, relate in particular to a kind of technology by etherificate and aromatization reformulated gasoline.
Background technology
" world fuel charter " delivered in the 3rd world fuel meeting, proposed worldwide gasoline and bavin and do not had standard.Partial content sees Table 1.
| 1 grade | 2 grades | 3 grades | |
| Octane number, RON MON lead content/g/L (maximum) oxygen content (%) (maximum) sulfur content (ppm) hydrocarbon forms aromatic hydrocarbons/%v/v benzene content/%v/v olefin(e) centent/%v/v | 91，95，98 82，85，88 0.013 2.7 1000 50 5 | 91; 95,98 82.58588 do not fill perhaps leading 200 40 2.5 20 | 91; 95,98 82.58588 do not fill perhaps leading 30 35 1 10 |
In order to adapt to the development of world fuel, China implements " motor spirit objectionable impurities control criterion " (hereinafter to be referred as " standard ") in the part city, ban use of doped fuel and No. 70 gasoline.This standard requires in the recent period: 1) sulphur content is not more than 0.08%m/m; 2) olefin(e) centent does not lie in 35%v/v;
3) benzene content is not more than 2.5%v/v; 4) aromaticity content is not more than 40%v/v.
And the catalytically cracked gasoline content of China accounts for 79% of gasoline total amount at present, and catalytic reforming gasoline only accounts for 5%.China's gasoline mainly contains following characteristics:
(1) aromaticity content is lower in the gasoline
Reformed gasoline accounts for 5% in China's gasoline, and reformed gasoline passes through the aromatic hydrocarbons extracting again mostly, so aromaticity content is low, and 90
#The white gasoline aromaticity content only is about 10%.
(2) olefin(e) centent height in the gasoline
Catalytically cracked gasoline ratio height makes olefin(e) centent greater than 40% in China's gasoline.
(3) oxygen level is low
The oxygen of proper content helps improving the burning of gasoline in the gasoline.
Analyze and find, improve the present gasoline quality of China, most important approach is to reduce olefin(e) centent in the gasoline, and does not reduce the octane value of gasoline.
Catalytically cracked gasoline is owing to contain a large amount of alkene, thereby higher octane value is arranged.If adopt the method for direct hydrogenation to handle, then normal olefine hydrogenation generation normal paraffin octane value reduces too big.If but generated aromatic hydrocarbon, octane value also could raise.With four carbon pentaene hydrocarbon of the carbon in the petroleum naphtha and pure etherificate, being converted into gasoline also is a kind of selection preferably.
Above-mentioned etherificate and aromatization modification gasoline are carried out combined optimization, be about to the light constituent etherification of olefine, heavy constituent alkene aromizing, upgrading catalytically cracked gasoline well.
At present low carbon olefin hydrocarbon etherification there are some patents.
Chinese patent 94110775.2 is technology and the equipment that a kind of reaction distillation is produced ether, the catalysis-distillation equipment that adopts is selected the hydrogenation and removing diolefin simultaneously, the etherification reaction of tertiary olefin and Fatty Alcohol(C12-C14 and C12-C18) and product separation, reactive distillation column divides three sections of upper, middle and lowers, the conversion zone at middle part comprises two mixed phase reaction zones and a catalytic distillation zone, be provided with two middle fractionation zones in the reaction zone simultaneously, catalyzer is in bulk, and is easy to loading and unloading.
Chinese patent 96109509.1 relates to a kind of etherification of olefine catalysts and method for making thereof, catalyzer is made up of active metal component, promotor and carrier, active metal component is metals such as Pt, Ni, Pd, Co, Cu, and carrier is an acidic cation-exchange resin.Because the soluble salt of having selected the 3rd main group element in the periodic table of elements and/or the 4th main group element for use is as promotor, therefore this catalyzer is being used for C
3～C
7In etherification of olefins reaction and/or the selective hydrogenation, have long and selective hydrogenation and the active advantages of higher of double-bond isomerization of stable high life.
Chinese patent 97105845.8 relates to a kind of technology that makes tertiary olefin etherificate in carbon five and the above hydrocarbon raw material thereof.It utilize light hydrocarbon can with C#-[4] following alcohols forms the characteristics of azeotrope, makes reaction residue methyl alcohol and carbon five formation azeotropes, between reactor and azeotropic distillation column or catalytic distillation tower, circulate, thereby saved methanol recovery system.
Chinese patent 00123948.1 is catalyzer and the application thereof that a kind of propylene hydration etherificate is produced ether and alcohol.This catalyzer is to adopt one or more organic acid to the β Zeolite modifying, and the modified beta zeolite catalyst of preparation has significantly improved the transformation efficiency of propylene hydration etherification reaction and the selectivity of diisopropyl ether.This patent also discloses catalyzer and has produced application in the technology of ether and alcohol in the propylene hydration etherificate.
Chinese patent 00103383.2 is a kind of C#-[5 of being rich in]～C#-[7] catalyst etherifying method for light hydrocarbon of isomeric olefine, comprise light hydrocarbon feedstocks and alcohol under 20～95 ℃, 1.0～4.0MPa, contact with catalyst for etherification with the condition of isomeric olefine mol ratio 1.0～1.2: 1 by alcohol, the composition of wherein said catalyst for etherification comprises the β zeolite of 60～80 heavy %, the inorganic oxide of 10～30 heavy % and the fluorine of 1.0～10.0 heavy %.This method is suitable for the degree of depth etherificate of FCC petroleum naphtha, can improve the octane value of gasoline component and increase oxygen level.
U.S. Pat 4854939 is carried out etherificate earlier with carbon four raw materials, carries out fractionation by distillation then, and with cat head distilled unreacted methyl alcohol and aromatization of hydrocarbons completely, the product after bottoms and the aromizing is exactly the gasoline that obtains.
At present to the more existing researchs of the aromizing of gasoline.
Chinese patent 93102129.4 relates to a kind of catalytic modification of poor quality gasoline aromatization method that is used for.Going into first step reactor through the stock oil of preheating contacts with catalyzer, carry out the catalytic reforming reaction under certain condition, obtain octane value (MON) and reach performance-oriented gasoline component more than 80, comprise≤gas stream of C4 goes into second stage reactor through preheating and contacts with catalyzer, carry out aromatization under certain condition, obtain aromatic hydrocarbons mixture and the gas that is rich in hydrogen.
The method of a Chinese patent 98117812.X catalytic aromatization of gasoline fraction, be to make stock oil after the preheating and water vapor in fluidized-bed reactor, contact with the microspherical catalyst that contains the five-ring supersiliceous zeolite of heat, at temperature 500-650 ℃, pressure 0.15-0.40MPa, weight hourly space velocity 1-6h
-1, agent-oil ratio 5-15: 1, water-oil ratio 0.05-0.5: react under 1 the condition; Reaction product, water vapor and treat that regenerated catalyst carries out gas solid separation; The product liquid that reaction product isolated obtains being rich in the gaseous product of propylene and butylene and is rich in aromatic hydrocarbons; Treat that regenerated catalyst Returning reactor behind water vapor stripping and coke burning regeneration recycles.The characteristics of this method are to adopt the successive reaction-reprocessing cycle operating method of fluidized-bed reactor and the conveying of catalyzer fluidised form to carry out aromatization.
The catalysis conversion method of 99109194.9 1 kinds of gasoline upgradings of Chinese patent, be that the bottom of the low octane value gasoline after the preheating from riser tube entered, highly olefinic gasoline enters from the middle part of riser tube or the bottom of fluidized-bed, contacts with catalyzer, and reaction back effluent enters settling vessel; Reaction product isolated, reclaimable catalyst returns riser tube and recycles after stripping, regeneration.Adopt method provided by the invention, the alkene during gasoline is formed can be reduced to 20 heavy %, and the isoparaffin during gasoline is formed can be increased to more than the 30 heavy %, and the RON of gasoline is about 90.
The hydrogenation modification method of 99122229.6 1 kinds of gasoline fractions of Chinese patent comprises the gasoline fraction of sulfur-bearing and hydrogen and a kind of catalyzer contact reacts, and described catalyzer contains one or more and the alumina host in molybdenum and/or tungsten, nickel and/or cobalt, auxiliary agent magnesium, macropore and the mesopore zeolite; In oxide compound and with the total catalyst weight is benchmark, and the content of molybdenum and/or tungsten is that the content of 3-20 heavy %, nickel and/or cobalt is that the heavy % of 0.3-2, auxiliary agent Mg content are the heavy % of 1-7, and the content of zeolite is the heavy % of 5-60.This method does not significantly reduce gasoline octane rating and liquid yield when reducing the gasoline fraction sulphur content, and more simple.
The method of 00109374.6 1 kinds of modifying catalytically cracked gasolines of Chinese patent, it is characterized in that making catalytically cracked gasoline in riser reactor, to contact, at the weight ratio 3-15 of temperature of reaction 300-600 ℃, reaction pressure 130-450kpa, reaction times 1-6 second, catalyzer and catalytically cracked gasoline: 1, the weight ratio 0.01-0.3 of water vapor and catalytically cracked gasoline: react under 1 the condition with the solid acid catalyst that contains the five-ring mesopore zeolite; Reaction product isolated; Reclaimable catalyst stripping, regeneration back Returning reactor internal recycle use.This method can reduce olefin(e) centent, maleic value and the nitrogen content of catalytically cracked gasoline, and the by-product low-carbon alkene.
Summary of the invention
The object of the present invention is to provide a kind of technology by etherificate and aromatization reformulated gasoline.
To achieve these goals, the technical solution used in the present invention is: low-carbon alkene in the petroleum naphtha component and alcohols are carried out etherification reaction; Simultaneously alkene in the heavy petrol component is carried out aromatization in addition.Two kinds of reacted products are mixed, obtain the gasoline that olefin(e) centent is low and octane value is high.
Concrete steps of the present invention are:
1) earlier gasoline is distilled, be divided into the petroleum naphtha component A and the above heavy petrol B component of carbon six hydrocarbon of main carbon containing four carbon five hydro carbons.
Wherein the carbon number of petroleum naphtha component A is formed and to be distributed as: carbon four accounts for 1-20%, and carbon five accounts for 60-85%, and carbon accounts for no more than 20% more than six.
The group composition of petroleum naphtha component A is distributed as: alkane accounts for 15-75%, and alkene accounts for 15-75%, and other accounts for and is not more than 10%.
The ingredients constitute of carbon below six no more than 30% of heavy petrol B component.
2) alkene in the petroleum naphtha component and alcohols carry out etherification reaction, and temperature of reaction is 20-300 ℃, and pressure is 0.1-5.0MPa, and air speed is that every gram catalyzer per hour advances 0.1-20 gram oil, and the catalyzer of use can be resin, molecular sieve and heteropolyacid; Alkene is 0.1-30 with the mol ratio of alcohol: 1; The alcohols of reaction usefulness can be methyl alcohol, ethanol, propyl alcohol, Virahol.
3) the heavy petrol B component separately or enter aromatization reactor with hydrogen and carry out aromatization, employed catalyzer is the modified catalyst of one or more and these molecular sieve of ZSM-5, ZSM-11, ZSM-12, ZSM-35, MCM-22, Y molecular sieve or beta-molecular sieve; Temperature of reaction is 100-500 ℃, and pressure is 0.1-8.0MPa, and air speed is that every gram catalyzer per hour advances 0.1-20 gram oil.
4) can purge regeneration by high temperature in air atmosphere behind the molecular sieve catalyst inactivation that adopts in the step 2 and 3, regeneration temperature 100-550 ℃, pressure is 0.1-5.0MPa, and the volume space velocity of air is 50-10000h
-1Regeneration atmosphere also can be nitrogen oxygen atmosphere or oxygen, and wherein oxygen concentration is 1-100%, and regeneration temperature 100-550 ℃, pressure is 0.1-5.0MPa, and the volume space velocity of air is 50-10000h
-1
Behind the resin and heteropolyacid catalyst inactivation that adopts, regenerate with solvent wash, solvent for use can for carbon number less than 5 alcohols, acetone, the alkane of carbon number 5 to 10, the aromatic hydrocarbons of carbon number 6 to 10.
5) step 2 and 3 reacted products are mixed, obtain the gasoline C that olefin(e) centent is low and octane value is high.The content of ether is 0.1-10% among the stop bracket gasoline C, and aromaticity content is 15-40% in the gasoline, and wherein benzene is less than 2.5%, and alkane is 20-60%, and olefin(e) centent is less than 20%, and Study of Gasoline method octane is 70-120.
Embodiment
Below by example in detail the present invention is described in detail.
(%) composed as follows of the catalytically cracked gasoline raw material that example is used:
The composition of the full cut of catalytically cracked gasoline is: normal paraffin: 4.86%, and isoparaffin 30.65%, alkene: 40.69%, naphthenic hydrocarbon: 7.07%, aromatic hydrocarbons: 16.35%, octane value (RON): 89.8.
Catalytically cracked gasoline is through after the fractionation, be divided into account for total amount 20% less than 70 ℃ lighting end and account for total amount 80% greater than 70 ℃ last running.It is composed as follows:
Lighting end: normal paraffin 6.19%, isoparaffin 41.53%, alkene 51.22%, naphthenic hydrocarbon 0.85%, aromatic hydrocarbons 0.19%.
Last running: normal paraffin 4.56%, isoparaffin 28.29%, alkene 37.79%, naphthenic hydrocarbon 8.60%, aromatic hydrocarbons 20.51%.
Example 1
Under the catalysis of the Tricesium dodecatungstophosphate catalyzer of silica gel load, above-mentioned petroleum naphtha component and methyl alcohol are carried out etherification reaction.Reaction conditions is: temperature of reaction is 70 ℃, and pressure is 1.0MPa, and air speed is that every gram catalyzer per hour advances 1.0 gram oil, and the mol ratio of alkene and methyl alcohol is 2: 1.
Above-mentioned heavy petrol component is carried out aromatization, adopt the ZSM-5 molecular sieve, molecular sieve was through 550 ℃ of steam-treated two hours.Reaction conditions is: 400 ℃ of temperature of reaction, reaction pressure 5.0MPa, air speed 10.0h
-1
After the reaction above-mentioned two kinds of reaction product are mixed, the weight of mixed product oil consists of: normal paraffin: 6.84%, isoparaffin 25.78%, alkene: 8.34%, naphthenic hydrocarbon: 3.52%, aromatic hydrocarbons: 50.16%, ethers: 4.55%, octane value (RON): 99.0, it is 95% that oil is received.
Example 2
Under the catalysis of beta-molecular sieve catalyzer, above-mentioned petroleum naphtha component and ethanol are carried out etherification reaction.Reaction conditions is: temperature of reaction is 90 ℃, and pressure is 3.0MPa, and air speed is that every gram catalyzer per hour advances 1.0 gram oil, and alkene and alcoholic acid mol ratio are 5: 1.
Above-mentioned heavy petrol component is entered aromatization reactor carry out aromatization after hydrogen mixes, adopting the ZSM-11 molecular sieve is catalyzer, and molecular sieve was through 550 ℃ of steam-treated two hours.Reaction conditions is: 350 ℃ of temperature of reaction, reaction pressure 2.0MPa, hydrogen to oil volume ratio 300, air speed 2.0h
-1
After the reaction above-mentioned two kinds of reaction product oil are mixed, the weight of mixed product oil consists of: normal paraffin: 6.84%, isoparaffin 28.78%, alkene: 16.34%, naphthenic hydrocarbon: 5.52%, aromatic hydrocarbons: 35.16%, ethers: 1.25%, octane value (RON): 92.0, it is 98% that oil is received.
Example 3
Under the catalysis of ZSM-5 molecular sieve catalyst, make wherein alkene and propyl alcohol carry out etherification reaction above-mentioned petroleum naphtha component.Reaction conditions is: temperature of reaction is 110 ℃, and pressure is 2.0MPa, and air speed is that every gram catalyzer per hour advances 1.0 gram oil, and the mol ratio of alkene and propyl alcohol is 10: 1.
Above-mentioned heavy petrol component is carried out aromatization, and adopting the ZSM-5 molecular sieve of La modification is catalyzer, through 520 ℃ of 3h of water vapor place.Reaction conditions is: temperature of reaction is 350 ℃, and reaction pressure is 1.8MPa, and weight space velocity is 1.8h
-1
After the reaction above-mentioned two kinds of reaction product are mixed, the weight of mixed product oil consists of: normal paraffin: 9.84%, isoparaffin 32.78%, alkene: 16.84%, naphthenic hydrocarbon: 5.52%, aromatic hydrocarbons: 33.16%, ethers: 1.05%, octane value (RON): 92.5, it is 97% that oil is received.
Example 4
Under the catalysis of acid cation exchange resin catalyst, make wherein alkene and Virahol carry out etherification reaction above-mentioned petroleum naphtha component.Reaction conditions is: temperature of reaction is 90 ℃, and pressure is 2.0MPa, and air speed is that every gram catalyzer per hour advances 1.0 gram oil, and the mol ratio of alkene and Virahol is 20: 1.
Above-mentioned heavy petrol component is carried out aromatization, is catalyzer with MCM-22 and ZSM-35 cocrystallization molecular sieve at 500 ℃ of following steam treatment 3h.Reaction conditions is: temperature of reaction is 315 ℃, and reaction pressure is 1.8MPa, and weight space velocity is 1.7h
-1
After the reaction above-mentioned two kinds of reaction product are mixed, the weight of mixed product oil consists of: normal paraffin: 11.14%, isoparaffin 39.28%, alkene: 19.34%, naphthenic hydrocarbon: 7.02%, aromatic hydrocarbons: 22.16%, ethers: 0.25%, octane value (RON): 90.0, it is 99% that oil is received.
Example 5
The catalyst for etherification ZSM-5 molecular sieve of inactivation in the example 3 and the ZSM-5 molecular sieve of aromatized catalyst La modification (contain weight percentage be 0.8% La) are regenerated in air, and air pressure is 1.8MPa, and volume space velocity is 5000h
-1, regeneration temperature is 540 ℃, and the recovery time is 1h, reacts under the condition identical with example 3 through the catalyzer after the regeneration, and the regeneration rear catalyst is active basic identical with live catalyst.
Example 6
With the catalyst for etherification resin of example 4 inactivations in reactor by regenerating with methanol wash.
The aromatized catalyst MCM-22 of example 4 inactivations and ZSM-35 cocrystallization molecular sieve heated up in nitrogen causes 530 ℃ of constant temperature, switches then to cause to feed the nitrogen oxygen atmosphere that contains 1% oxygen, and pressure is 1.8MPa, and volume space velocity is 5000h
-1, the content of the carbonic acid gas in the detection tail gas.When the content of the carbonic acid gas in the tail gas was lower than 0.1%, switching caused and feeds the nitrogen oxygen atmosphere that contains 2% oxygen, detects the content of the carbonic acid gas in the tail gas.When the content of the carbonic acid gas in the tail gas was lower than 0.1%, switching caused and feeds the nitrogen oxygen atmosphere that contains 5% oxygen, detects the content of the carbonic acid gas in the tail gas.When the content of the carbonic acid gas in the tail gas was lower than 0.1%, switching caused and feeds the nitrogen oxygen atmosphere that contains 10% oxygen, detects the content of the carbonic acid gas in the tail gas.When the content of the carbonic acid gas in the tail gas was lower than 0.1%, switching caused bubbling air, continues constant temperature 3h then.
React under the condition identical with example 4 through the catalyzer after the regeneration, the regeneration rear catalyst is active basic identical with live catalyst.
The present invention is not limited only to above example.In a word, can the upgrading catalytically cracked gasoline by etherificate and aromatization, obtain the gasoline that olefin(e) centent is low and octane value is high.
Claims (9)
1, a kind of technology by etherificate and aromatization reformulated gasoline, its step is
A) earlier gasoline is distilled, be divided into the petroleum naphtha component A and the above heavy petrol B component of carbon six hydrocarbon of main carbon containing four carbon five hydro carbons;
B) alkene in the petroleum naphtha component and alcohols carry out etherification reaction, and temperature of reaction is 20-300 ℃, and pressure is 0.1-5.0MPa, and air speed is that every gram catalyzer per hour advances 0.1-20 gram oil, and the catalyzer that uses is resin, molecular sieve or heteropolyacid; Alkene is 0.1-30 with the mol ratio of alcohol: 1;
C) the heavy petrol B component enters aromatization reactor and carries out aromatization, and employed catalyzer is the modified catalyst of molecular sieve and molecular sieve; Temperature of reaction is 100-500 ℃, and pressure is 0.1-8.0MPa, and air speed is that every gram catalyzer per hour advances 0.1-20 gram oil;
D) behind the catalyst deactivation that adopts among step b and the c, recycle through manipulation of regeneration;
E) two kinds of reacted products are mixed, obtain the gasoline C that olefin(e) centent is low and octane value is high.
2, by the described technology of claim 1, it is characterized in that the carbon number of described petroleum naphtha component A is formed and is distributed as: carbon four accounts for 1-20%, and carbon five accounts for 60-85%, carbon is more than six no more than 20%;
The group composition of petroleum naphtha component A is distributed as: alkane accounts for 15-75%, and alkene accounts for 15-75%, and other is no more than 10% years old.
3, by the described technology of claim 1, it is characterized in that the component of carbon below six no more than 30% of described heavy petrol B component.
4, by the described technology of claim 1, it is characterized in that described alcohols is methyl alcohol, ethanol, propyl alcohol or Virahol.
5, by the described technology of claim 1, it is characterized in that described heavy petrol B component enters aromatization reactor with hydrogen and carries out aromatization.
6, by the described technology of claim 1, it is characterized in that described heavy petrol B component is carried out the improved catalysts that the employed catalyzer of aromatization is one or more and these molecular sieve of ZSM-5, ZSM-11, ZSM-12, ZSM-35, MCM-22, Y molecular sieve or beta-molecular sieve.
7, by the described technology of claim 1, it is characterized in that the content of ether is 0.1-10% among the gained stop bracket gasoline C, aromaticity content is 15-40% in the gasoline, and wherein benzene is less than 2.5%, and olefin(e) centent is less than 20%, and Study of Gasoline method octane value is 70-120.
By the described technology of claim 1, it is characterized in that 8, described catalyzer purges regeneration by high temperature in air, nitrogen oxygen or oxygen atmosphere, regeneration temperature 100-550 ℃, pressure is 0.1-5.0MPa, and the volume space velocity of air is 50-10000h
-1
9, by the described technology of claim 1, it is characterized in that resin and heteropolyacid catalyst are regenerated with solvent wash behind the described inactivation, solvent for use is a carbon number less than 5 alcohols, acetone, the alkane of carbon number 5 to 10 or the aromatic hydrocarbons of carbon number 6 to 10.
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101497826B (en) * | 2008-12-31 | 2012-09-26 | 山西华顿实业有限公司 | Catalytic modifying production process for methanol fuel |
| CN102746875B (en) * | 2011-04-20 | 2014-08-13 | 中国石油化工股份有限公司 | New method for preparation of gasoline from ethanol |
| CN102839021A (en) * | 2011-06-22 | 2012-12-26 | 北京金伟晖工程技术有限公司 | Device and method for preparing low-sulfur high-octane gasoline at low cost |
| CN102633585A (en) * | 2012-02-03 | 2012-08-15 | 南京迈森科技发展有限公司 | Method for preparing high-purity propane, iso-butane and n-butane |
| CN103509591B (en) * | 2012-06-28 | 2015-07-29 | 中国石油化工股份有限公司 | A kind of method of gasoline deep etherificate upgrading |
| CN106000457A (en) * | 2016-05-24 | 2016-10-12 | 山东成泰化工有限公司 | Composite catalyst used for gasoline etherification and preparation method thereof |
| CN105944754A (en) * | 2016-05-24 | 2016-09-21 | 山东成泰化工有限公司 | Light oil etherification catalyst and preparation method thereof |
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