CN1115386C - Method for raising induction period of gasoline - Google Patents
Method for raising induction period of gasoline Download PDFInfo
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- CN1115386C CN1115386C CN 00132749 CN00132749A CN1115386C CN 1115386 C CN1115386 C CN 1115386C CN 00132749 CN00132749 CN 00132749 CN 00132749 A CN00132749 A CN 00132749A CN 1115386 C CN1115386 C CN 1115386C
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- gasoline
- waste residue
- hydrogen
- hydrogenation
- residue oil
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Abstract
The present invention relates to a method for raising an induction period of gasoline, which is characterized in that a gasoline raw material and hydrogen gas enter a fixed bed reactor to be in contact with a hydrogenation catalyst of waste slag oil, the gasoline raw material and the hydrogen gas and the hydrogenation catalyst of waste slag oil are reacted under operating conditions that hydrogen partial pressure is from 1.0 to 8.0MPa, a reaction temperature is from 150 to 300 DEG C, volume air speed is from 1.0 to 10.0h<-1>, and a volume ratio of hydrogen to oil is from 100 to 500Nm<3>/m<3>, a reaction is separated, and gas rich in hydrogen gas returns the reactor for circulating use. The induction period of the gasoline product obtained by the method exceeds 480 minutes of the requirement of high-grade gasoline specification, and the loss of the octane number of a research method is not greater than 1 unit.
Description
The invention belongs to a kind of is the method that obtains the refining hydrocarbon ils of low boiler cut existing under the situation of hydrogen, more particularly, is that a kind of depleted residual oil hydrocatalyst that utilizes carries out selective hydrogenation to improve the method for breakdown time to inferior patrol.
Deep Catalytic Cracking process is a kind of deep catalytic cracking method that is the main purpose product with voluminous gas alkene, also produce simultaneously a part of catalytic cracking gasoline, catalytic cracking gasoline has higher octane value, research octane number (RON) (following brief note RON) generally can reach more than 98, is the good stop bracket gasoline blend component of a kind of potential performance.But catalytic cracking gasoline contains unstable compounds such as diolefine, so its oxidation stability is poor, and generally be no more than 250 minutes inductive phase, does not meet the requirement of specification gasoline.
Can make the diene in the catalytic cracking gasoline saturated by the hydrogenation means, thereby improve its stability, improve inductive phase, but wish that one of main contributor of catalytic cracking gasoline octane value-alkene is the least possible saturated and make loss of octane number minimum simultaneously again.Therefore, just need carry out selective hydrogenation to catalytic cracking gasoline.The process for selective hydrogenation process adopts palladium type and nickel type hydrogenation catalyst usually.They have good activity and a selectivity to diolefin hydrogenation is saturated, but sulfur resistance is relatively poor, concerning nickel type hydrogenation catalyst, requires in the stock oil sulphur content below 200ppm, and precious metals palladium catalyst is more responsive to sulphur, and a spot of sulphur just can influence its activity and life-span in the stock oil.And because Deep Catalytic Cracking process is raw material with the mink cell focus, so the sulphur of catalytic cracking gasoline, nitrogen content are higher usually, sulphur content can reach 1000ppm even higher, so palladium type and nickel type hydrogenation catalyst can not be handled the so high catalytic cracking gasoline of sulfur-bearing.
CN1109495A discloses a kind of Rifining method for catalylic cracking gasoline by adding hydrogen, this method is with two kinds of fresh prevulcanized type non-precious metal catalyst series connection with variable grain diameter, segmentation is contained in the reactor or is divided in two reactors, at 150～300 ℃ of temperature, hydrogen dividing potential drop 1.2～8.0MPa, volume space velocity 4～20h
-1And 1～15h
-1, volume of hydrogen oil ratio 150～500Nm
3/ m
3, turning oil and fresh feed weight of oil be than 0.5～5: carry out hydrogenation reaction under 1 the operational condition.The maleic value of hydrogenated products is less than 1gI
2/ 100g, inductive phase surpass 480 minutes, loss of octane number is not more than 3 units.
Residual hydrogenation can be produced the low sulphur fuel oil that meets the environmental regulation requirement.Residual oil is the mixture that crude distillation goes out the high-boiling hydrocarbons behind the light-end products, residual most of sulphur, nitrogen and impurity such as most metal and bituminous matter in the crude oil, so the residual hydrogenation reaction process is more more complicated, difficult than the distillate hydrogenation reaction.In the residual hydrogenation there be the main reaction that takes place: hydrogenating desulfurization (HDS), hydrodenitrification (HDN), hydrodemetallation (HDM) (HDM), hydrocracking and heat cracking reaction etc.Residual hydrogenation needs harsh operational condition, and promptly higher hydrogen dividing potential drop, temperature of reaction and lower volume space velocity, particularly volume space velocity have only 0.15～0.35h usually
-1, far below the air speed of distillate hydrogenation process.When lower volume space velocity means the stock oil of handling same amount, need in the residual hydrogenation reactor to load a large amount of catalyzer, that is to say that the refinery needs a large number of expense of expense to buy residual oil hydrocatalyst.With 2,000,000 tons/year residual hydrogenation equipment of a cover is example, and catalyzer Intake Quantity is about 550～600 tons in the reactor, and catalyst costs is about 380～4,500,000 dollars.And the more important thing is, because plurality of heavy metal and bituminous matter deposit and coking on catalyzer in the residual hydrogenation reaction process, make residual oil hydrocatalyst very short work-ing life, have only 6 months to 1 year time usually.The catalyst deactivation that is caused by metal deposition is irreversible, promptly can not catalyzer be reused by the regenerated mode.Therefore, after each residual hydrogenation equipment is stopped work and changed agent, all there is a large amount of discarded catalyzer to wait for refinery's cost thought considers how to handle.Contain more poisonously and contain the material of heavy metal in the depleted residual oil hydrocatalyst, generally simply it is buried or fills out the sea, certainly will pollute environment.EP555128 considers to adopt the technology of metal recovery to handle, but complex process spends also higher.
The objective of the invention is to provide on the basis of existing technology a kind of method that improves breakdown time, this method will improve induction period of gasoline, and its loss of octane number is very little simultaneously.
Method provided by the invention is: gasoline stocks and hydrogen enter fixed-bed reactor, contact with the waste residue oil hydrogenation catalysts, at hydrogen dividing potential drop 1.0～8.0MPa, 150～300 ℃ of temperature of reaction, volume space velocity 1.0～10.0h
-1, hydrogen to oil volume ratio 100～500Nm
3/ m
3Operational condition under react, reaction product isolated, the gas Returning reactor that is rich in hydrogen recycles.
Described gasoline stocks inductive phase was less than 480 minutes, this class gasoline has catalytic cracking gasoline, pressure gasoline and coker gasoline etc., wherein catalytic cracking gasoline comes from Deep Catalytic Cracking process, this gasoline contains unstable compounds such as diolefine, therefore its oxidation stability is poor, and generally be no more than 250 minutes inductive phase.Because Deep Catalytic Cracking process is raw material with the mink cell focus, so the sulphur of catalytic cracking gasoline, nitrogen content are higher usually, sulphur content can reach 1000ppm even higher, requires hydrogenation catalyst to have stronger sulfur poisoning-resistant ability.
Hydrogenation for the gasoline stocks of low inductive phase is saturated, wishes only to make an one double-bond hydrogenation saturated and be converted into monoolefine, does not wish that it further saturatedly becomes alkane and lose octane value.It is faster than monoolefin hydrogenation saturated reaction speed that diolefin hydrogenation generates the speed of response of monoolefine, therefore can adopt active also not really high catalyzer to reach the purpose of selective hydrogenation.
The catalyzer that is used for the gasoline stocks selective hydrogenation of low inductive phase should require to have following two characteristics: (1), higher sulfur poisoning-resistant ability; (2), suitable hydrogenation activity and selectivity preferably.And the waste residue oil hydrogenation catalysts can satisfy this 2 requirements basically.At first waste residue oil hydrogenation catalysts itself just contains a large amount of sulphur, and live catalyst also is to re-use after sulfuration, does not therefore have the problem of sulfur poisoning; And the still residual certain hydrogenation activity of waste residue oil hydrogenation catalysts requires lower low inductive phase of gasoline selective hydrogenation process applicable to hydrogenation activity.
The waste residue oil hydrogenation catalysts comes from the residual hydrogenation process, and this catalyzer needn't be regenerated, needn't be through prevulcanized before the catalytic cracking gasoline hydrogenation.At present the active metal component of residual oil hydrocatalyst is selected from a kind of in nickel-tungsten, nickel-tungsten-cobalt, nickel-molybdenum or the cobalt-molybdenum, and carrier is selected from a kind of in aluminum oxide, silicon-dioxide or the amorphous silicon aluminium.
But, the residual hydrogenation process is to some particular requirement of physical properties of catalyzer, as need a certain proportion of mesopore to macropore and higher pore volume, and can arrive the activity of such catalysts surface with the macromole that satisfies the residual oil medium-high viscosity and react, can hold a large amount of metals and coke again simultaneously.In reaction process and since metal and coke on catalyzer deposition and covered the activity of such catalysts center gradually and its duct narrowed down, cause the active loss of catalyst reaction.Can not satisfy the refinery when requiring when activity of such catalysts drops to hydrogenated products, just will be drawn off more and change.The waste residue oil hydrogenation catalysts is still residual certain hydrogenation activity, compares with live catalyst, and residual activity approximately is 10～40% of a live catalyst.The waste residue oil hydrogenation catalysts contains 1～50% heavy metal Ni, V and Fe and 5～30% coke usually, and the pore volume and the specific surface area of catalyzer reduce significantly, and typical spent catalyst pore volume only is 0.1～0.5mL/g, and specific surface area is 10～100m
2/ g.Sedimentary metal all exists with the sulfide state on the catalyzer, as V
3S
4, Ni
3S
2Deng.And be deposited on V on the catalyzer
3S
4The catalyst pores structure is changed, and it also have certain high active of hydrogenation catalysis.Therefore, the waste residue oil hydrogenation catalysts still has certain hydrogenation activity to utilize, but should not be used for the technological process that hydrogenation activity is had relatively high expectations.
Method provided by the invention has made full use of the residual hydrogenation activity of waste residue oil hydrogenation catalysts, make that diolefine is converted into monoolefine in the gasoline stocks of low inductive phase, increase substantially induction period of gasoline, surpassed 480 minutes that top grade product specification gasoline requires inductive phase; For catalytic cracking gasoline, its loss of octane number is very little, and the RON loss is not more than 1 unit.Therefore, the gasoline component that this method can the production good security, octane value is high.The waste residue oil hydrogenation catalysts is used further to the gasoline selective hydrogenation, prolonged the work-ing life of residual oil hydrocatalyst, and because the waste residue oil hydrogenation catalysts has deposited a large amount of coke, though hydrogenation activity is not high, but very stable, so its deactivation rate is lower than conventional selective hydrogenation catalyst.The cost of waste residue oil hydrogenation catalysts is than conventional selective hydrogenation catalyst much less, for an effective outlet is found in the processing of waste residue oil hydrogenation catalysts.
The following examples will give further instruction to method provided by the invention, but not thereby limiting the invention.
Embodiment
Test is to carry out on the fixed bed hydrogenation testing apparatus of a 250mL.Test used waste residue oil hydrogenation catalysts RF-220 (being produced by Dutch Aksu chemical company) and turned round nearly 3000 hours in a residual hydrogenation test before this test, its main character is listed in table 1.Testing used raw material is catalytic cracking gasoline, and its main character is listed in table 2.
After waste residue oil hydrogenation catalysts RF-220 removes fine powder through simply sieving, in the reactor of directly packing into.Before the feeding catalytic cracking gasoline carries out hydropyrolysis experiment, do not carry out prevulcanized.Catalytic cracking gasoline and hydrogen are at reactor inlet hydrogen dividing potential drop 3.2MPa, 250 ℃ of temperature of reaction, volume space velocity 2.0h
-1, hydrogen to oil volume ratio 500Nm
3/ m
3Condition under react, reaction product isolated obtains gasoline fraction.The main character of gasoline fraction is listed in table 2.
As can be seen from Table 2, catalytic cracking gasoline maleic value before hydrogenation is 5.8gI
2/ 100g, only be 122 minutes inductive phase.Catalytic cracking gasoline is given birth to olefiant maleic value and is dropped to 0.1gI behind hydrogenation
2Below/the 100g, be more than 1000 minutes inductive phase, considerably beyond specification gasoline desired 480 minutes, and RON has only lost 0.3 unit.
Table 1
| Catalyzer | Fresh RF-220 | Useless RF-220 |
| Chemical constitution, heavy % | ||
| MoO 3 | 6.5 | - |
| NiO | 1.2 | - |
| Specific surface area, m 2/g | 141 | 74 |
| Pore volume, mL/g | 0.70 | 0.18 |
| Foreign matter content, heavy % | ||
| S | - | 14.6 |
| C | - | 7.2 |
| Ni | - | 4.2 |
| V | - | 18.1 |
| Fe | - | 0.1 |
Table 2
| Project | Gasoline stocks | Gasoline products |
| Density (20 ℃), g/cm 3 | 0.7976 | 0.7954 |
| Refractive index (20 ℃) | 1.4558 | 1.4546 |
| Sulphur, heavy % | 2230 | 2020 |
| Nitrogen, heavy % | 48 | 47 |
| The bromine valency, gBr/100g | 59 | 47 |
| Maleic value, gI 2/100g | 5.8 | ＜0.1 |
| Inductive phase, minute | 122 | ＞1000 |
| Octane value | ||
| MON | 84.7 | 84.7 |
| RON | 99.0 | 98.7 |
Claims (8)
1, a kind of method that improves breakdown time is characterized in that gasoline stocks and hydrogen enter fixed-bed reactor, contacts with the waste residue oil hydrogenation catalysts, at hydrogen dividing potential drop 1.0～8.0MPa, 150～300 ℃ of temperature of reaction, volume space velocity 1.0～10.0h
-1, hydrogen to oil volume ratio 100～500Nm
3/ m
3Operational condition under react, reaction product isolated, the gas Returning reactor that is rich in hydrogen recycles.
2,, it is characterized in that described gasoline stocks inductive phase was less than 480 minutes according to the method for claim 1.
3,, it is characterized in that described gasoline stocks is catalytic cracking gasoline, pressure gasoline, coker gasoline or its mixture according to the method for claim 1 or 2.
4,, it is characterized in that described waste residue oil hydrogenation catalysts derives from the fixed bed residual hydrogenation equipment according to the method for claim 1.
5, according to the method for claim 1, the total pore volume that it is characterized in that the waste residue oil hydrogenation catalysts is 0.1～0.5mL/g.
6, according to the method for claim 1, the surface-area that it is characterized in that the waste residue oil hydrogenation catalysts is 10～100m
2/ g.
7,, it is characterized in that sedimentary total metal content is that the sedimentary metal of 1～50 heavy % comprises vanadium, nickel and/or iron on the waste residue oil hydrogenation catalysts according to the method for claim 2.
8, according to the method for claim 1, it is characterized in that the waste residue oil hydrogenation catalysts needn't regenerate before use, also needn't prevulcanized.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 00132749 CN1115386C (en) | 2000-11-17 | 2000-11-17 | Method for raising induction period of gasoline |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 00132749 CN1115386C (en) | 2000-11-17 | 2000-11-17 | Method for raising induction period of gasoline |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1354225A CN1354225A (en) | 2002-06-19 |
| CN1115386C true CN1115386C (en) | 2003-07-23 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 00132749 Expired - Fee Related CN1115386C (en) | 2000-11-17 | 2000-11-17 | Method for raising induction period of gasoline |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103695035B (en) * | 2012-09-28 | 2015-08-26 | 中国石油化工股份有限公司 | A kind of combined method of producing super low-sulfur oil |
| CN103710045B (en) * | 2012-09-28 | 2016-01-20 | 中国石油化工股份有限公司 | A kind of method of producing super low-sulfur oil |
| KR102385590B1 (en) | 2014-07-17 | 2022-04-11 | 사빅 글로벌 테크놀러지스 비.브이. | Upgrading hydrogen deficient streams using hydrogen donor streams in a hydropyrolysis process |
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Granted publication date: 20030723 Termination date: 20111117 |