CN1026331C - Etherification process method of olefin-containing gasoline - Google Patents
Etherification process method of olefin-containing gasoline Download PDFInfo
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- CN1026331C CN1026331C CN 89105065 CN89105065A CN1026331C CN 1026331 C CN1026331 C CN 1026331C CN 89105065 CN89105065 CN 89105065 CN 89105065 A CN89105065 A CN 89105065A CN 1026331 C CN1026331 C CN 1026331C
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- 238000000034 method Methods 0.000 title claims abstract description 23
- 238000006266 etherification reaction Methods 0.000 title claims abstract description 21
- 150000001336 alkenes Chemical class 0.000 title abstract description 6
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title abstract description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 54
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000004523 catalytic cracking Methods 0.000 claims abstract description 8
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000002253 acid Substances 0.000 claims abstract description 4
- 239000003729 cation exchange resin Substances 0.000 claims abstract description 4
- 238000000197 pyrolysis Methods 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 238000005516 engineering process Methods 0.000 claims description 9
- 239000002994 raw material Substances 0.000 claims description 8
- 239000003208 petroleum Substances 0.000 claims description 6
- 239000003381 stabilizer Substances 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 3
- 238000003672 processing method Methods 0.000 claims 1
- 238000000926 separation method Methods 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- 238000011160 research Methods 0.000 abstract description 7
- 238000004939 coking Methods 0.000 abstract description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 abstract 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 28
- 239000003054 catalyst Substances 0.000 description 15
- 238000002156 mixing Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 238000009835 boiling Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 230000002779 inactivation Effects 0.000 description 2
- 230000001939 inductive effect Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000007337 electrophilic addition reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000004508 fractional distillation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 210000000952 spleen Anatomy 0.000 description 1
- HVZJRWJGKQPSFL-UHFFFAOYSA-N tert-Amyl methyl ether Chemical compound CCC(C)(C)OC HVZJRWJGKQPSFL-UHFFFAOYSA-N 0.000 description 1
- 238000006276 transfer reaction Methods 0.000 description 1
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- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Liquid Carbonaceous Fuels (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
An etherification process method of olefin-containing gasoline, which utilizes the characteristic that coking gasoline, pyrolysis gasoline and catalytic cracking gasoline are rich in olefin to improve the octane number. It is characterized by that it is mixed with a certain quantity of methanol, passed through an expanded bed reactor, and undergone the process of catalytic etherification under the catalytic action of sulfonic acid type macroporous strong acid cation exchange resin, and the etherified light gasoline and non-etherified heavy gasoline are blended so as to obtain the etherified gasoline. The process can improve the research octane number by 1.8-31 units, improve the stability and reduce the vapor pressure.
Description
The present invention instigates olefine contained gasoline directly to carry out the etherificate upgrading.Improve its octane value, reduce its vapour pressure and bromine valency simultaneously, improve the novel process of stability.The characteristics of this technology are that process is simple, operational condition relaxes, energy consumption is low, do not contend over raw materials with other process, improve the many-sided performance of product.
The octane value that improves motor spirit is one of important topic of current refining of petroleum.Methyl tertiary butyl ether (MTBE) and tert amyl methyl ether(TAME) (MTAE) are developed rapidly as gasoline high-octane rating admixture in recent years.Technology about this respect has been done a large amount of research both at home and abroad, and existing industrial production device, and its raw material comes vent one's spleen C in the body of catalytic cracking
4C in cut and the gasoline
5Cut, C
4Be the valuable raw material of petrochemical complex, and C
5Itself be exactly gasoline fraction, thus MTBE produced and the MTAE raw material sources are restricted, thereby be used for gasoline (call in 5～10% heavy MON of making and improve 1～3 unit) as the high-octane rating blending component and can not satisfy the demand.
English Patent 1249016 has been revealed the etherified gasoline production process, and it is to fractionate out one＜77 ℃ to contain C from the overhead product of cracking case
4～C
6The tertiary olefin cut, simultaneously these alkene carry out etherification reaction with lower alcohol on catalyst for etherification, and the cut of etherificate is concocted with other hydrocarbon fraction at least.Above-mentioned patent is also warned and can not be used wide boiling range cut, thinks that the improvement of gasoline octane rating will reduce greatly if use the material of boiling range broad.And there is a shortcoming in the etherification procedure that adopts narrow fraction, is exactly before and after the etherificate because separate raw materials and the big energy of product consumption are very uneconomical.
Patent Office of the People's Republic of China discloses " etherification technology of gasoline that the catalytic cracking of fluidized molecular sieve-bed hydrocarbon ils obtains " of CN87100930A in application on September 7th, 1988, this is applied for a patent and has changed traditional utilization blending high octane components and improve the octane value of gasoline, but the C that utilizes catalytic gasoline self to possess
4～C
8Tertiary olefin adds methanol etherification.This technology is that the catalytic gasoline distillation is cut into light and heavy two cuts, and lighting end adds methyl alcohol, through the fixed-bed reactor catalyst etherifying, produces the reactant and the above-mentioned last running blending that contain multiple methyl ether and forms.Above-mentioned technology is owing to adopt the fixed-bed reactor catalyst etherifying, and then in mass transfer and heat transfer reaction process, the homogeneity of mass transfer is affected, and also can impel the local generation of reactor batch temperature overheated, causes the catalyst overheating inactivation.The table 1 that provides in above-mentioned application specification, table 2 data, residual methanol amount contained in its etherified gasoline are up to 5～10%, minimum＞3%.Just can improve the RON(research octane number (RON) of gasoline in this case) 0.5～2.6 unit, test according to Beijing Research Institute of Petro-Chemical Engineering, only in catalytically cracked gasoline, add methyl alcohol 5～10%, can improve RON1.7～3.6 unit, if the effect of deduction methyl alcohol, then the RON value that improves owing to etherificate is just very little, and the price of methyl alcohol is more much higher than gasoline, also has not a leg to stand on economically.Above-mentioned in addition technical process is complicated, and practicality is relatively poor.
The object of the invention is to utilize catalytically cracked gasoline to be rich in the characteristics of isomeric olefine, makes it and methanol etherification, produce to contain ether gasoline, and boosting of octane rating, technical process simultaneously is simple, and production cost is low.
The object of the present invention is achieved like this.With the full cut (30～200 ℃) of coker gasoline or pyrolysis gasoline or catalytically cracked gasoline or catalytically cracked gasoline after cutting in the lighting end of (do is 80～120 ℃), after adding a certain amount of methyl alcohol, catalyst etherifying in expanded bed reactor, etherification temperature is in 40～110 ℃ of scopes, and petroleum naphtha behind catalyst etherifying and unetherified heavy gasoline are allocated and the generation etherified gasoline.Above-mentioned methanol usage accounts for 3～10%(body of catalyst etherifying feed gasoline), 3～6%(body preferably).Catalyzer in the expanded bed reactor is a sulfonated polystyrene macropore strong acid cation exchange resin.
Etherification reaction mechanism: more isomeric olefine is arranged in the catalytically cracked gasoline, under the effect of an acidic catalyst, be easy to electrophilic addition reaction and methyl alcohol and generated corresponding ethers, reaction formula is as follows:
The present invention is owing to adopted expanded bed reactor to carry out the catalyst etherifying reaction, bed volume has expanded one times than fixed bed, and the catalyst etherifying reaction is thermopositive reaction, and the speed of response of bed is controlled easily, the mass-and heat-transfer that helps reaction process makes reactor batch temperature even.Avoid catalyzer local superheating inactivation.Behind catalyst etherifying, methyl alcohol almost all is converted into ether.The residual amount of methyl alcohol is less than 1% in the gasoline.Not only can improve the octane value of gasoline after the etherificate, and can reduce the bromine valency of gasoline, increase its inductive phase, thereby improve the stability of gasoline.Reduce vapour pressure.Help storing and using.This flow process can adopt the stabilizer tower of catalytic cracking device to open the charging of the light gasoline fraction of 30～100 ℃ of side line extractions as etherification procedure, does not set up distillation tower cutting stock oil.Make process simplification and save energy.The present invention is not only applicable to catalytically cracked gasoline in addition, and coker gasoline, pyrolysis gasoline are suitable for too.
Below in conjunction with schema specific embodiments of the present invention is described further:
Referring to Fig. 1, the stabilizer tower of catalytic cracking device (opening side line) is extracted out less than the charging as etherification procedure of 100 ℃ light gasoline fraction, methyltertiarvbutyl ether reactor is an expanded bed, and raw material light gasoline fraction and methyl alcohol are in 100: 3～6(volume) ratio autoreactor bottom enters.Hydrogen macropore strong acid cation exchange resin is housed in the reactor, and temperature of reaction is controlled at 60～80 ℃, reaction pressure 0.8～1.0MPa, liquid hourly space velocity 3～5hr
-1, pure oil volume is than best 0.03～0.06.After mixing, the heavy petrol that the reaction product of coming out from reactor top is come out with the stabilizer tower bottom is etherified gasoline after cooling off.Wherein ether content is that 3～5%(is heavy), residual methanol＜1%, research octane number (RON) improves 1.5～3.0 units.Bromine valency and vapour pressure reduce.Catalyzer shows that through longevity test continuous operation is 2000 hours under top condition, and ether content still remains on about 7% in the gasoline, and catalyst activity does not have obvious downtrending, and testing data of life-span sees Table 1.
When being coker gasoline or catalytic gasoline of whole fraction as raw material, flow process and Fig. 1 are basic identical.Only the former charging is from coking fractional distillation column, for overhead product is told gasoline behind the coking gas in gas-liquid separator after cooling off; The latter is the gasoline at the bottom of the catalytic cracking stabilizer tower.This moment, side line do not left by stabilizer tower.Above-mentioned two kinds of situations with compare with petroleum naphtha etherificates before 100 ℃.Catalyst life is shorter, and the full cut lifetime data of catalytic gasoline sees Table 2.
Example 1: the full cut of coker gasoline (42～213 ℃) is sent into expanded bed reactor and is reacted, at 70 ℃ of temperature of reaction, air pressure 1.0MPa, volume space velocity 5hr after being mixed in proportion by coker gained and methyl alcohol
-1, alcohol/oil=3/100 condition under, the ether amount that contains of gained etherified gasoline is that 1.03%(is heavy), be increased to 365～475 minute by 230 minutes inductive phase, existent gum is a 2mg/100ml oil.Octane value also slightly improves.
Example 2: the full cut of catalytically cracked gasoline (40～191.5 ℃) etherificate in device shown in Figure 1.65 ℃ of temperature of reaction, air pressure 0.5MPa, volume space velocity 7hr
-1It is that 3.3%(is heavy that alcohol/oil=3/100, gained etherified gasoline contain the ether amount), research octane number (RON) (RON) is increased to 90 by 88.2, has a net increase of 1.8 units.
Example 3: after catalytic cracking petroleum naphtha (IBP～100 ℃) carries out etherificate by device shown in Figure 1, help cut etherified gasoline (IBP～196 ℃) with catalytically cracked gasoline (100～196 ℃) blending again, it contains the ether amount is 5%, and research octane number (RON) RON has a net increase of 3.1 units.
The relation of petroleum naphtha catalyst for etherification runtime and ether content before 100 ℃
Table 1
Sequence number hours ether content % sequence number hours ether content %
1 96 8.63 11 1128 8.20
2 192 8.84 12 1224 6.70
3 264 8.83 13 1320 6.69
4 360 8.85 14 1416 6.75
5 480 7.49 15 1512 7.13
6 570 7.00 16 1608 6.83
7 696 8.62 17 1728 7.31
8 768 8.05 18 1824 6.98
9 888 7.11 19 1968 7.43
10 1008 8.77 20 2016 7.31
Etherification conditions: T=65 ± 5 ℃ P=1.0MPa SV=3hr
-1Meoh/oil=4/100V
Catalytic gasoline of whole fraction catalyst for etherification runtime and ether content relation
Table 2
Sequence number hours ether content % sequence number hours ether content %
1 96 4.48 7 384 2.72
2 144 4.38 8 456 1.50
3 210 4.05 9 504 4.33
4 240 4.03 10 552 1.75
5 312 4.45 11 600 1.18
6 360 3.50 12 624 0.89
Claims (4)
1, a kind of olefine contained gasoline etherification technology method that improves coker gasoline, pyrolysis gasoline, catalytically cracked gasoline octane value, it is characterized in that adding at the full cut of olefine contained gasoline or in doing to 80-120 ℃ lighting end with the gasoline volume ratio be the methyl alcohol of 0.03-0.1, be that 40-110 ℃, reaction pressure 0.8-1.0MPa, liquid hourly space velocity are 3-5h in temperature of reaction
-1Carry out etherification reaction by the expanded bed reactor that the macropore strong acid cation exchange resin is housed under the condition, directly obtain etherified gasoline when being raw material, then mix obtaining etherified gasoline during with lighting end mutually with heavy petrol with full cut.
2, olefine contained gasoline etherification technology method according to claim 1 is characterized in that directly taking out side line and gets the processing method of petroleum naphtha to the etherificate expanded bed reactor, and do not set up separation column on the catalytic cracking unit stabilizer tower.
3, olefine contained gasoline etherification technology method according to claim 1 is characterized in that full cut is meant 30-200 ℃ gasoline.
4, olefine contained gasoline etherification technology method according to claim 1, the volume ratio that it is characterized in that methyl alcohol and gasoline is 0.03-0.06.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 89105065 CN1026331C (en) | 1989-04-22 | 1989-04-22 | Etherification process method of olefin-containing gasoline |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 89105065 CN1026331C (en) | 1989-04-22 | 1989-04-22 | Etherification process method of olefin-containing gasoline |
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| Publication Number | Publication Date |
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| CN1046549A CN1046549A (en) | 1990-10-31 |
| CN1026331C true CN1026331C (en) | 1994-10-26 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN 89105065 Expired - Fee Related CN1026331C (en) | 1989-04-22 | 1989-04-22 | Etherification process method of olefin-containing gasoline |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1051478C (en) * | 1996-08-21 | 2000-04-19 | 中国石化齐鲁石油化工公司 | Catalyst for etherification of olefine and preparing process thereof |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101245259B (en) * | 2007-02-14 | 2011-01-19 | 中国石油化工股份有限公司石油化工科学研究院 | A hydrocarbon etherification method combined with a catalytic cracking absorption stabilization system |
| CN101245258B (en) * | 2007-02-14 | 2011-08-10 | 中国石油化工股份有限公司 | Etherification method integrated with catalytic cracking absorption stable system |
| CN101245255B (en) * | 2007-02-14 | 2012-05-30 | 中国石油化工股份有限公司 | Etherification method for producing clean gasoline |
| CN101245257B (en) * | 2007-02-14 | 2011-04-20 | 中国石油化工股份有限公司 | Sidetrack etherification method integrated with catalytic cracking absorption stable system |
| CN101270301B (en) * | 2007-03-23 | 2011-04-20 | 中国石油天然气股份有限公司 | A light gasoline etherification process and catalytic cracking gasoline upgrading method containing the process |
| CN102618329B (en) * | 2011-01-31 | 2014-06-04 | 北京安耐吉能源工程技术有限公司 | Gasoline processing method |
| CN102688774B (en) * | 2012-05-30 | 2014-04-02 | 凯瑞化工股份有限公司 | Resin catalyst for light gasoline etherification and preparation method thereof |
| CN103571532B (en) * | 2013-11-26 | 2015-05-27 | 凯瑞环保科技股份有限公司 | Pre-etherification reaction method in light petrol etherification technology |
| CN112898121A (en) * | 2021-01-23 | 2021-06-04 | 四川上氟科技有限公司 | Preparation method of perfluoroalkyl alcohol |
-
1989
- 1989-04-22 CN CN 89105065 patent/CN1026331C/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1051478C (en) * | 1996-08-21 | 2000-04-19 | 中国石化齐鲁石油化工公司 | Catalyst for etherification of olefine and preparing process thereof |
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| Publication number | Publication date |
|---|---|
| CN1046549A (en) | 1990-10-31 |
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