CN101506334A

CN101506334A - A hydrocarbon desulfurization process

Info

Publication number: CN101506334A
Application number: CN200680055639.3A
Authority: CN
Inventors: V·P·塔卡尔
Original assignee: Universal Oil Products Co
Current assignee: Universal Oil Products Co
Priority date: 2006-07-19
Filing date: 2006-07-19
Publication date: 2009-08-12
Anticipated expiration: 2026-07-19
Also published as: EP2041245A4; CA2657780C; EP2041245A1; CN101506334B; WO2008010799A1; RU2009105660A; CA2657780A1; RU2402594C1

Abstract

A process for the production of low sulfur hydrocarbonaceous products. The hydrocarbon feedstocks are processed in integrated desulfurization zone (3), hydrocracking (21) and hydrogenation zones (22) to produce ultra low sulfur diesel (38), low sulfur naphtha products (37) and low sulfur heavy distillate (17).

Description

A kind of method of hydrocarbon sweetening

Background of invention

The present invention relates to the field of hydrocarbon feed desulfurization to lower level.Petroleum refinement factory has used hydrodesulfurization to be used to produce the hydrocarbon flow that more for example petroleum naphtha, gasoline, kerosene and the diesel oil etc. of high value have lower concentration sulphur and nitrogen.The most frequent raw material by hydrotreatment or desulfurization is generally liquid hydrocarbonaceous streams for example petroleum naphtha, kerosene, diesel oil, gas oil, vacuum gas oil (VGO) and topping wet goods.On the convention, the processing intensity of hydrogenating desulfurization selects to depend on that sufficient improvement is to produce marketable product or to be suitable for the raw material of downstream processing.For many years, people have recognized for environmental consideration and new regular regulations of working out, and salable product must satisfy for example restriction of sulphur and nitrogen of more and more lower pollutent.Recently be used for for example new regulations of gasoline and diesel oil of transport fuel what US and European had proposed that actual needs removes desulfuration fully from liquid hydrocarbon.

Usually, desulfurization can by when hydrogen exists under the temperature and pressure condition that raises, hydrocarbon feed contacts with the desulfurization catalyst that suits and finishes the product that contains the highest required sulphur of placing restrictions on generation in desulfurization reaction vessel or district.Operational condition in desulphurization reactor and desulfurization catalyst influence the quality of desulfurization product.

Although schema is varied, operational condition and catalyzer have been applied in the commercial sulfur removal activity, need the new sulfur method with low-cost required product quality always.When producing the low-sulfur transport fuel, method of the present invention has improved the economic benefit of producing low-sulfur fuel greatly.

Information disclosure

US 5,114, and 562 B1 disclose a kind of method, and wherein the hydrotreatment of middle distillate petroleum streams process is to produce low-sulfurs and low aromatic product at two placed in-line reaction zones.The ejecta of first reaction zone is carried by hydrogen and is removed hydrogen sulfide and pass through the indirect heat exchange reheat then.Second reaction zone uses the noble metal hydrogenation catalyst to sulfur sensitive.

Summary of the invention

The present invention relates to a kind of improved method that is used to produce low sulfur hydrocarbonaceous products.First hydrocarbon feed be contained in be higher than 343 ℃ of ebullient hydrocarbon components and hydrogen in the reaction of first desulfurization zone to produce the first desulfurization zone ejecta, it introduces the liquid hydrocarbonaceous streams that steam-liquid trap contains the vapor stream of more lower boiling hydrocarbon compound and hydrogen and contains the hydrocarbon component of the sulphur concentration with reduction with generation in the temperature that raises.Contain the vapor stream of more lower boiling hydrocarbon compound, hydrogen and be contained in second hydrocarbon feed that is lower than 371 ℃ of ebullient hydrocarbon components and react the hydrocracking zone ejecta of introducing hydrogenation zone simultaneously with ebullient hydrocarbon recycle stream in 149 ℃ to 371 ℃ scopes to produce, produce the preferably hydrocarbon flow of ebullient super low sulfur in 149 ℃ to 371 ℃ scopes to produce by fractionation at hydrocracking zone.The liquid hydrocarbonaceous streams fractionation that provides by steam-liquid trap is to produce preferably in 149 ℃ to 371 ℃ scopes ebullient hydrocarbon recycle stream and to be contained in the liquid hydrocarbonaceous streams of the sulphur that is higher than 371 ℃ of ebullient hydrocarbon components and concentration that have reduction.

Other embodiment of the present invention comprises for example type of feed and explanation, desulfurization catalyst, hydrocracking catalyst and preferably comprises the further details of the operational condition of temperature and pressure, and all these are open in the following discussion aspect these each of the present invention.

Accompanying drawing is the simplified flow chart of the preferred embodiments of the invention.

Detailed Description Of The Invention

Have been found that the more effective and more economical super-low sulfur hydrocarbon products that comprises the ultra-low-sulphur diesel raw material Production can realize in above-mentioned Unionfining desulfurization and hydrocracking process use.

According to the present invention, preferably be contained in the component that is higher than 343 ℃ of boilings and more preferably be higher than The component of 371 ℃ of boilings, and for example contain AGO (atmospheric gas oil), vacuum gas oil, cracking gas oil, Coking distillate thing, straight run distillate thing, solvent-deasphalted oils, pyrolysis-derived oils, higher boiling artificial oil and Catalytic cracking distillates first raw material of introducing first desulfurization zone of thing. Preferred raw material is gas oil or its It heats up in a steamer branch and the most common the temperature between 315 ℃ to 538 ℃ in other of weight at least 50% The component of degree boiling is in weight at least 75%.

First desulfurization zone reaction that contains desulfurization catalyst that first raw material and hydrogen are being operated under desulfurization condition.Preferred desulfurization condition comprises that liquid hourly space velocity from 204 ℃ to 482 ℃ temperature and hydrocarbon charging is from 0.1hr ^-1To 10hr ^-1

The suitable desulfurization catalyst that uses in the present invention is that any known traditional hydrotreating catalyst and comprising contains at least a VIII family metal, preferred iron, cobalt and nickel, more preferably those of cobalt and/or nickel and at least a VI family metal, preferred molybdenum and tungsten, and it is on high surface area carrier material, preferred aluminum oxide.Other suitable desulfurization catalyst comprises zeolite catalyst, and noble metal catalyst, and wherein precious metal is selected from palladium and platinum.Scope of the present invention be included in use in the same reaction vessel more than a kind of desulfurization catalyst.Usually VIII family metal has the amount of from 2 to 20 weight percentage ranges, preferably from 4 to 12 weight percents.Usually VI family metal has the amount of from 1 to 25 weight percentage ranges, preferably from 2 to 25 weight percents.Typical desulfurization temperature is from 204 ℃ to 482 ℃ scope, and pressure is from 2.1MPa to 17.3MPa, preferably from 2.1MPa to 13.9MPa.

The ejecta that obtains from first desulfurization zone is introduced preferably in the steam-liquid displacement zone that is higher than 288 ℃ of operations with vapor stream that hydrogeneous, hydrogen sulfide and the highest more lower boiling 371 ℃ of ebullient hydrocarbon compounds are provided and first liquid hydrocarbonaceous streams that is contained in the sulphur of the concentration that is higher than 371 ℃ of ebullient hydrocarbon components and has reduction.First liquid hydrocarbonaceous streams also is contained in the part of ebullient hydrocarbon in 149 ℃ to the 371 ℃ scopes, it preferably introduces hot flash zone, introduce cold flash zone then and with aftercut the hydrocarbon recycle stream that is contained in from 149 ℃ to 371 ℃ of ebullient hydrocarbon to be provided and to be contained in second liquid hydrocarbonaceous streams of the sulphur of the concentration that is higher than 371 ℃ of ebullient hydrocarbon components and has reduction.This second liquid hydrocarbonaceous streams preferably is used as the suitable raw material of fluid catalytic cracking process.Hydrogeneous, hydrogen sulfide and more lower boiling the highest be admitted in the vapor stream of 371 ℃ of ebullient hydrocarbon compounds with at second hydrocarbon feed that is lower than 371 ℃ of ebullient hydrocarbon components contain hydrocracking catalyst hydrocracking zone to produce the hydrocracking zone ejecta.Second hydrocarbon feed can be any suitable be lower than 371 ℃ of boilings and ebullient raw material in 177 ℃ to 371 ℃ scopes preferably.The raw material that these are suitable for example, comprises hydrocarbon, coking overhead product and the light cycle of straight run middle distillate, kerosene and diesel oil boiling range.

Hydrocracking zone can contain one or more beds identical or different catalysts.In one embodiment, when preferred product was middle distillate, preferred hydrocracking catalyst used and one or more VIII or amorphous basic thing of group vib metal hydrogenation component bonded or low-level molecular sieve basis thing.In another embodiment, when preferred product during in the gasoline boiling range, the general hydrocracking zone that contains catalyzer comprises any crystalline zeolite cracking basis thing of the VIII family metal hydrogenation component of sedimentary small part on it.Other hydrogenation component may be selected from the bonded group vib with the zeolite base thing.Zeolite as cracking basis thing refers to molecular sieve sometimes and generally comprises silicon oxide, aluminum oxide and one or more tradable positively charged ions for example sodium, magnesium, calcium, alkaline-earth metal etc. in the literature.They further characterize by the crystal pores between the diameter of 4 to 14 dusts relatively uniformly.The preferred use has the high relatively zeolite between 3 to 12 silica.The suitable zeolite that has been found that at nature comprises, for example, and mordenite, stilbite, heulandite, ferrierite, dachiardite, chabazite, erionite and faujusite.Suitable synthetic zeolite comprises, for example, and B, X, Y and L crystal type, for example, synthetic faujasites and mordenite.Preferred zeolite is those of crystal pore diameters with 8-12 dust, and wherein the mol ratio of silica is 4 to 6.The example of preferred zeolite is synthetic Y molecular sieve in preferred kind.

The zeolite of natural generation is typically na form, alkaline earth metal form or its mixed form.The synthetic zeolite nearly all is to prepare with na form earlier.Under any circumstance, in order to use as a kind of cracking basis thing, preferred great majority or whole original zeolite monovalence metal and polyvalent metal and/or ammonium ion exchange, its heating by subsequently with decompose with zeolite bonded ammonium ion with hydrogen atom and/or by further except that anhydrating and the exchange site of decationizingization stays.Hydrogen or this natural " decationizingization " Y molecular sieve be at US-A-3, describes especially in 130,006.

Blended polyvalent metal-hydrogen zeolite can by at first with ammonium salt ion-exchange, then the part with the polyvalent metal salt anticommuting and then the calcining prepare.In some cases, as under the situation of synthesizing flokite, hydrogen form can be by the direct acid treatment preparation of alkali metal zeolites.Preferred cracking basis thing be based on initial loading capacity at least 10%, preferred those of at least 20% metal cation deficient.The zeolite of special kind that wish or stable be wherein at least 20% loading capacity by satisfied those of hydrogen ion.

In the preferred hydrocracking catalyst of the present invention, use as the active metal of hydrogenation component and be those of VIII family, i.e. iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium and platinum.Except these metals, also can use and these bonded promotors, comprise the group vib metal, for example, molybdenum and tungsten.The quantity of the hydrogenation metal in catalyzer can change within a large range.Broadly, can use 0.5 to 30% any amount by weight.In the example of precious metal, usually preferably use 0.05 to 2 weight percent.With hydrogenation metal bonded preferable methods is to contact in the aqueous solution of the suitable compound of required metal with the zeolite base thing, and wherein metal exists with cationic form.The hydrogenation metal that brings Selection In then, the catalyst fines that filter then, drying obtains, with the compressing tablet of (if necessary) such as the lubricant that adds, binding agents, and for deactivated catalyst and decompose ammonium ion in air at for example 371 °-648 ℃ temperature lower calcination.Perhaps, zeolite component is compressing tablet at first, adds hydrogenation component then and passes through calcining and activating.Above-mentioned catalyzer can use under the form of non-dilution, or can the mixed powder zeolite catalyst with at other relative SA catalyzer, thinner or the binding agent of 5 to 90 weight percentage ranges (for example aluminum oxide, silica gel, silica-alumina are cogelled, activated clay etc.) and compressing tablet altogether.These thinners can so use or they can contain the hydrogenation metal for example VIB and/or the VIII metal of the adding of small part.

Additional metals helps hydrocracking catalyst also in the method for the invention available, and it comprises, for example, and aluminophosphate molecular sieve, crystalline chromosilicates and other crystalline silicate.Crystallization chromium silicon oxide is at US-A-4, describes in 363,718 comprehensively.

Hydrocracking is implemented when hydrogen exists and preferably under cracking conditions, and it comprises from (232 ℃) to 468 ℃ temperature, the pressure from 3548kPa to 20785kPa, liquid hourly space velocity (LHSV) from 0.1 to 30hr ^-1, and the hydrogen speed of circulation is from 337 standard m ³/ m ³To 4200 standard m ³/ m ³

Preferably in 232 ℃ to 371 ℃ scope ebullient hydrocracking zone ejecta and hydrocarbon recycle stream preferably directly feed contain hydrogenation catalyst hydrogenation zone to produce the hydrogenation zone ejecta.Hydrogenation catalyst can be selected from any known hydrogenation or desulfurization catalyst.This catalyzer is can be with the desulfurization catalyst that uses at desulfurization zone identical or different and can be selected from known desulfurization catalyst, for example those that above describe in the example.Preferred hydroconversion condition can be selected from for the scope of desulfurization zone explanation and can compare higher, lower or harsh in the same manner with the reaction conditions that desulfurization zone is selected.

Cold steam-liquid displacement zone that the hydrogenation zone ejecta partial concentration that obtains and being introduced in is operated under 21 ℃ to the 60 ℃ temperature is to produce rich hydrogenous hydrogen sulfide containing gas streams and liquid hydrocarbonaceous streams.The rich hydrogenous gas streams that obtains preferably pass the sour gas washing section with the concentration that reduces hydrogen sulfide to produce the rich hydrogenous gas streams of purifying, their parts wherein can be as desired or needed recirculation then.Come the liquid hydrocarbonaceous streams of self cooling steam-liquid trap preferably to introduce cold flash drum to remove dissolved hydrogen and to be generally the hydrocarbon of gas and to enter fractionation zone subsequently to produce doctor negative diesel product stream.Preferred diesel product stream contains the sulphur that is lower than 50wppm, more preferably the sulphur of 10wppm.Make-up hydrogen can be introduced flow process in any suitable position.

With reference now to accompanying drawing,, the feed steam that contains heavy vacuum gas oil enters flow process by line 1 and mixes with the hydrogenous gas streams that provides by line 28 of richness, and the mixture that obtains is introduced desulfurization zones 3 by line 2.Quenching hydrogen adds desulfurization zone by line 30 and 31.Carry and introduce heat steam-liquid trap 5 from the ejecta that desulfurization zone 3 obtains by line 4.The gas streams of the hydrocarbon of hydrogeneous, hydrogen sulfide and low boiling range remove from heat steam-liquid trap 5 by line 17 and with transmit by line 18 and mix in middle distillate scope ebullient light cycle, and the mixture that obtains is carried by line 19 and is introduced reactor 20, and wherein materials flow contacts with hydrocracking zone 21.The ejecta that hydrocracking zone 21 obtains is directly sent into the hydrogenation zone 22 that is contained in the reaction zone 20.The ejecta that hydrogenation zone 22 obtains transmits and introduces heat exchanger 24 by line 23.Cold steam-liquid trap 26 is removed and introduced to the materials flow of the cold and partial condensation that obtains by line 25 from heat exchanger 24.Rich hydrogenous materials flow is removed by line 27 from cold steam-liquid trap 26 and is introduced desulfurization zone by above-mentioned

line

28,29,30 and 31.Cold flash drum 33 is removed and introduced to liquid hydrocarbonaceous streams from cold steam-liquid trap 26 by line 32.Gas streams hydrogeneous and that be generally the hydrocarbon of gas is removed from cold flash drum 33 by line 34.Fractionation zone 36 is removed and introduced to the liquid stream that contains the hydrocarbon of diesel boiling range by line 35 from cold flash drum 33.The diesel stream of super low sulfur is regained and is removed by line 38 from fractionation zone 36.Containing the hydrocarbon flow that boiling point is lower than the compound of diesel boiling range removes and regains by line 37 from fractionation zone 36.Hot flash drum 7 is removed and introduced to liquid stream from heat steam-liquid trap 5 by line 6.Hydrogeneous and remove and regain by line 8 from hot flash drum 7 than the vapor stream of lower boiling hydrocarbons.The liquid hydrocarbonaceous streams that is contained in the hydrocarbon that is higher than 371 ℃ of ebullient hydrocarbon and diesel boiling range is removed by line 9 and is introduced and the mixture that obtains is introduced gas by line 10 and carried district 11 with the above-mentioned vapor stream of passing through line 34 and providing of this paper from hot flash drum 7.The hydrocarbon flow of hydrogeneous, as the to be generally gas hydrocarbon and the hydrocarbon of gasoline boiling range is carried district 11 from gas and is removed and regain by line 12.The liquid hydrocarbonaceous streams that is contained in the hydrocarbon that is higher than 371 ℃ of ebullient hydrocarbon and diesel boiling range is carried district 11 by line 13 from gas and is removed and introduce fractionation zone 14.Contain than the materials flow of low boiling hydrocarbon and remove and regain from fractionation zone 14 by line 15.Containing the liquid hydrocarbonaceous streams that is higher than 371 ℃ of ebullient hydrocarbon removes and regains from fractionation zone 14 by line 17.Above-mentioned reaction zone 20 is removed and be incorporated herein to the liquid stream that contains the hydrocarbon of diesel boiling range by line 16 from fractionation zone 14.

Advantage and the benefit by using them to provide that comprises by method of the present invention clearly has been provided for above-mentioned description and synoptic diagram.

Claims

1, a kind of method that is used for two kinds of hydrocarbon feed desulfurization comprises following step:

(a) make and contain first hydrocarbon feed (1) of hydrocarbon component and the hydrogen (28) that boiling point is higher than 343 ℉ and in the desulfurization zone of under desulfurization condition, operating (3), react with production desulfurization zone ejecta (6) with desulfurization catalyst;

(b) the desulfurization zone ejecta is introduced in steam-liquid trap (5) of operating under the temperature that is higher than 288 ℃ with provide comprise hydrogen, hydrogen sulfide and the highest at 371 ℃ of ebullient than the vapor stream (17) of low boiling hydrocarbon compound be higher than 371 ℃ of ebullient hydrocarbon components and having first liquid hydrocarbonaceous streams (6) of the sulphur concentration of reduction;

(c) with hydrogeneous, hydrogen sulfide and the highest 371 ℃ of ebullient than the low boiling hydrocarbon compound and the vapor stream (17) that is included in second hydrocarbon feed (18) that is lower than 371 ℃ of ebullient hydrocarbon components deliver to hydrocracking zone (21) to produce the hydrocracking zone ejecta;

(d) with the hydrocracking zone ejecta and in 149 ℃ to 371 ℃ scopes ebullient hydrocarbon recycle stream (16) deliver to hydrogenation zone (22) to produce hydrogenation zone ejecta (23);

(e) fractionation hydrogenation zone ejecta (23) is to be created in ebullient super low sulfur hydrocarbon flow (38) in 149 ℃ to the 371 ℃ scopes; With

(f) first liquid hydrocarbonaceous streams (6) regained in step (b) of fractionation is to produce in 149 ℃ to 371 ℃ scopes ebullient hydrocarbon recycle stream (16) and to be higher than 371 ℃ of ebullient hydrocarbon components and to have second liquid hydrocarbonaceous streams (17) of the sulphur concentration of reduction.

2, the method for claim 1, wherein first hydrocarbon (1) raw material is selected from the group of mainly being made up of atmospheric gas oil, vacuum gas oil, coking overhead product, cracked gasoil and its mixture.

3, method as claimed in claim 1 or 2, the operational condition that wherein is used for desulfurization zone (5) comprises temperature from 204 ℃ to 482 ℃, pressure from about 2.1MPa to 17.3MPa and the liquid air speed from 0.1hr ^-1To 10hr ^-1

4, as claim 1 or 2 or 3 described methods, the operational condition that wherein is used for hydrogenation zone (22) comprises temperature from 204 ℃ to 482 ℃, pressure from 2.1MPa to 17.3MPa and the liquid air speed from 0.1hr ^-1To 10hr ^-1

5, method according to any one of claims 1 to 4, wherein the super low sulfur hydrocarbon flow of producing in step (e) (38) contains the sulphur that is lower than 50wppm.

6, as each described method in the claim 1 to 5, wherein the super low sulfur hydrocarbon flow of producing in step (e) (38) contains the sulphur that is lower than 10wppm.

7, as each described method in the claim 1 to 6, wherein second raw material (18) is selected from the group of being made up of the hydrocarbon and the coking overhead product of light cycle, straight run middle distillate, kerosene and diesel boiling range.