CN104395435A - Methods for upgrading of contaminated hydrocarbon streams - Google Patents

Abstract

A method of upgrading a heteroatom-containing hydrocarbon feed by removing heteroatom contaminants is disclosed. The method includes contacting the heteroatom-containing hydrocarbon feed with an oxidant and an immiscible acid to oxidize the heteroatoms, contacting the oxidized- heteroatom- containing hydrocarbon feed with caustic and a selectivity promoter, and removing the heteroatom contaminants from the heteroatom-containing hydrocarbon feed. The oxidant may be used in the presence of a catalyst.

Description

The method of the contaminated hydrocarbon stream of upgrading

The cross reference of related application

The application is the sequence number submitted on December 23rd, 2010 is 12/977, the partial continuous case of 639 (name is called the method for the contaminated hydrocarbon stream of upgrading), 12/977, 639 be the sequence number submitted on October 14th, 2010 is 12/904, the partial continuous case of 446 (name is called the method for the contaminated hydrocarbon stream of upgrading), 12/904, 446 be the sequence number submitted on September 22nd, 2010 is 12/933, the partial continuous case of 898 (name is called sulfidation-oxidation catalyzer and using method thereof), 12/933, 898 require that the right of priority of the PCT/US08/82095 of " sulfidation-oxidation catalyzer and using method thereof " by name according to 35USC371 article, PCT/US08/82095 require that the temporary patent application 61/039 of " sulfidation-oxidation catalyzer and using method thereof " by name, the right of priority of 619, and the application is the sequence number submitted on September 22nd, 2010 is 12/888, the partial continuous case of 049 (product that name is called reaction system and obtains thus), in not inconsistent with disclosure of invention scope, the disclosure of every application is incorporated in text thus by reference.

Background technology

The application relates to the system and method for upgrading crude oil, refinery's intermediate flow and refinery products, fully to reduce the content of the heteroatoms pollutent undesirably obtained, and be conducive to reducing total acid value, increase American Petroleum Institute (API) AIP weight index number (api gravity).This heteroatoms pollutent includes but not limited to sulphur, nitrogen, phosphorus, Ni-V-Fe.The hydrocarbon feed streams by heteroatoms pollutes is made to carry out heteroatoms oxidation, generate containing oxidized heteroatomic hydrocarbon intermediate flow, then described stream is contacted with etching reagent with selectivity promotor, thus heteroatoms pollutent is removed from hydrocarbon stream, and thus relative to initial contaminated hydrocarbon feed streams, api gravity is increased, and total acid value reduces.

Well-known in the industry, the heteroatoms pollutent contained in crude oil includes but are not limited to sulphur, nitrogen, phosphorus, nickel, vanadium and iron and their acidic oxide, and the content of this heteroatoms pollutent can have a negative impact to the refining process of crude oil fractions.The heteroatoms mass percent that weight crude oil or enriched material contain is low to moderate 0.001%.On the contrary, the heteroatoms massfraction that contains of heavy crude is up to 5-7%.Along with the heteroatomic content of crude oil increases, its boiling point increases, and along with content of heteroatoms increase, api gravity reduces.These pollutents must remove in refining process, and to meet the environment regulations of the finished product specification (such as gasoline, diesel oil, crude oil), or preventing pollution thing makes the catalyst activity in the refining process of downstream, selectivity and survival time reduce.The such as pollutent of sulphur, nitrogen, phosphorus, Ni-V-Fe, and the total acid value (TAN) in crude oil fractions can have a negative impact etc. to Downstream processing, these Downstream processings comprise hydrotreatment, hydrocracking and catalytic cracking (FCC), only enumerate sub-fraction here.These pollutents are present in the crude oil fractions of various organic hydrocarbon molecule and different concns.

Because sulphur is disposed to the external world after combustion, cause environmental hazard, therefore sulphur is broadly considered the most outstanding heteroatoms pollutent.We believe, the oxysulfide that burning produces (is generically and collectively referred to as SO _xdischarge) exacerbate the formation of acid rain, and reduce the efficiency of catalytic converter in automobile.In addition, sulphur compound is considered to the fraction of particle considerably increasing products of combustion.Nitrogen, phosphorus and other heteroatoms pollutents all have similar environmental hazard.

In order to remove sulphur compound in the gas from the fuel before burning or post combustion emission, people have employed various method.Most of refinery using hydrogenating desulfurization (HDS) as the main method removing sulphur from hydrocarbon stream.For the sulfur-bearing lightweight stream of element sulfur content up to about 2% (w/w), HDS remains economic selection, but in heavy and acid stream (element sulfur content is greater than 2%), due to drop into reaction energy, make CO except the consumption of the high pressure needed for desulfuration and hydrogen ₂a large amount of discharge, environmental effect and the economic benefit of HDS are cancelled out each other.

Due to these problems, decreasing pollution thing, especially the sulphur content reduced in hydrocarbon stream has become the major objective of global environment method.In the U.S., in regulation road diesel oil, the peak concentration of sulphur is 15ppm.To in October, 2012, to non-road diesel oil, train diesel oil and marine diesel oil, sulfur-bearing standard will reach 15ppm.To in January, 2011, the standard of European Union to the diesel oil used in the equipment of inland waterways, the operation of road diesel oil and the equipment of non-road diesel oil operation is expected to be limited to 10ppm.By 2012, the standard of Chinese road diesel oil will be 10ppm.Standard the strictest is in the world in Japan at present, and the standard of there road diesel oil is 10ppm.

Purifier adopts catalytic desulfurhydrogenation (" HDS ", is often referred to hydrotreatment) method usually, reduces the content of sulphur in hydrocarbon fuel, reduces total acid value, increases api gravity.In hydrogenating desulfurization, from petroleum distillate, isolated hydrocarbon stream processes in the reactor, and the operating temperature of this reactor is between 575 to 750 ℉ (about 300 DEG C to about 400 DEG C).Hydrogen pressure be 430 to 14,500 pounds/square inch (3000 to 10,000kPa or 30 to 100atm), hourly space velocity is 0.5 to 4h ^-1.When the dibenzothiophene in feed and the catalyst exposure in fixed bed, dibenzothiophene and H-H reaction, this catalyzer comprises and is carried on VI race on aluminium and group VIII metal sulfide (such as, the sulfide of cobalt and molybdenum, or the sulfide of nickel and molybdenum).Due to the use of these operational conditionss and hydrogen, the capital investment of these methods and running cost are all very expensive.

Known at present, HDS or hydrotreatment can provide the process product meeting current strict sulphur standard.But thwarting the appearance of the sulphur compound removed owing to having space bit, the dibenzothiophene such as replaced, also there is other problems in this process.Such as, for the sulphur in the dibenzothiophene molecule that 4-alkyl in such as female ring replaces or 4-, 6-alkyl replaces, be just difficult to use this catalysis process Determination of Trace Sulfur to be eliminated.More generally, in heavier material, such as diesel oil and fuel oil, attempt the sulphur transforming these classes completely, thus cause equipment to spend increase, catalyzer is replaced more frequent, because side reaction causes product quality to decline, and continue to meet the most strict demand to some feed sulphur content.

This alternative impelling people to find non-hydrogen carrys out desulfurization, such as oxidation sweetening.One of mode of dealing with problems before discussed comprises by dibenzothiophene being oxidized to sulfone with oxygenant, optionally desulfurization is carried out to the dibenzothiophene in hydrocarbon stream, then selectively sulphones is separated from remaining hydrocarbon stream, and make sulfone and etching reagent react further, the part of sulfone is removed from hydrocarbon fragment.

Oxidation is considered to very useful, because a series of separating treatment can be used to be removed by oxidized sulphur compound, this separating treatment depends on the chemical property of change, such as sulphones water-soluble, volatility, and reactive.In application oxidation, an important consideration is exactly chemo-selective.Optionally sulfur oxide heteroatom moiety, and be not oxidized too much alkene and benzyl hydrocarbon in crude oil, refinery's intermediate product and refinery products, this is still very large challenge.Be in WO 2009/120238 A1 international application at the international publication number of Litz etc., disclose one optionally sulfoxidation method and system.The present inventor finds further, the catalyzer of above-mentioned international application can also be oxidized other heteroatomss, these heteroatomss include but are not limited to nitrogen and phosphorus, they, as containing in the crude oil of heteroatomic organic compounds, refinery's intermediate product and refinery products, are natural abundant pollutents.Fig. 1 is the list of the obtainable oxidation state of organic heteroatomic compound.

Another misgivings of heteroatoms oxidation are the process of the oxidized organic heteroatomic compound generated.If carry out hydrogen treatment to oxidized organic heteroatomic compound, original heteroatomic compound can be translated into, produce original problem thus.Content of heteroatoms in feed may be 0% to 10% for heteroatoms weight fraction.It is that be the replacement of 15% with non-substituted organic heteroatoms molecule that heteroatoms on average comprises weight fraction.Therefore, if oil is not removed from organic molecule, the high oil to 67% of weight fraction will be removed as the organic heteroatoms extract of oxidation.Process 40 for every day, the common refinery of 000 barrel of crude oil, every day can produce up to 27, and organic heteroatoms oil of the oxidation of 000 barrel, this has carried out conventional processing too much to as waste material.In addition, process oxidized organic heteroatoms oil and also waste valuable hydrocarbon, if can effectively process, this hydrocarbon is recycled in theory.

Concerning removal heteroatoms, a sizable challenge remains and remove oxidized heteroatoms fragment from organic heteroatomic compound of oxidation, and this oxidized organic heteroatomic compound is generated by organic heteroatoms kind that oxidation is original.Therefore, need certain methods and system, it carrys out the hydrocarbon feed streams that upgrading heteroatoms pollutes by being removed from hydrocarbon stream by heteroatoms pollutent, also has additional benefit: compared with contaminated hydrocarbon feed streams, and total acid value reduces, and the api gravity of end product increases.

Summary of the invention

The present invention relates to and carry out by removing heteroatoms pollutent the method that upgrading contains heteroatomic hydrocarbon stream, the method comprises: will contact containing heteroatomic hydrocarbon feed nitration mixture insoluble with at least one oxygenant and at least one; To contact with at least one selectivity promotor with at least one etching reagent containing oxidized heteroatomic hydrocarbon feed, heteroatoms pollutent will be removed from containing heteroatomic hydrocarbon feed.Oxygenant together can use with catalyzer.

The present invention further provides and a kind ofly carry out by removing heteroatoms pollutent the method that upgrading contains heteroatoms hydrocarbon stream, the method comprises: containing heteroatomic hydrocarbon feed and oxidising agent, to be oxidized heteroatoms pollutent at least partially, will form the first intermediate flow; Insoluble with at least one to first intermediate flow and at least one oxygenant nitration mixture is mixed, with the heteroatoms pollutent that oxidation is residual arbitrarily at least partially, form the second intermediate flow, second intermediate flow is contacted with at least one selectivity promotor with at least one etching reagent, to form the 3rd intermediate flow, described at least one selectivity promotor comprises the organic compound with at least one acid proton; To substantially not be separated from the 3rd intermediate flow containing heteroatomic hydrocarbon product; At least one etching reagent and at least one selectivity promotor is reclaimed from the second intermediate flow; At least one etching reagent that cycling and reutilization reclaims and at least one selectivity promotor.

The present invention also provides a kind of further and carrys out by removing heteroatoms pollutent the method that upgrading contains heteroatoms hydrocarbon stream, the method comprises and is oxidized to sulfone by containing the dibenzothiophene in heteroatomic feed, by described sulfone and insoluble nitration mixture and oxidising agent under the two-phase condition of oxidation, to remove heteroatoms pollutent at least partially, then by sulfone and etching reagent and selectivity booster response, and be separated and be substantially used for fuel containing heteroatomic hydrocarbon product.

With reference to following description, will be better understood other features of the present invention, aspect and advantage.

Accompanying drawing explanation

Technical characteristic of the present invention is set forth in the claims.But, by reference to the accompanying drawings, by referring to the detailed description of exemplified embodiment, better the present invention will be understood.Wherein:

Fig. 1 is according to the embodiment of the present invention, the diagram of some heteroatomic various oxidation state;

Fig. 2 is according to the embodiment of the present invention, before heteroatoms division, and the general flow figure of the embodiment of compound heteroatoms oxidising process;

Fig. 3 A is according to the embodiment of the present invention, before heteroatoms division, and the schema of the more detailed process of the embodiment of compound heteroatoms oxidising process;

Fig. 3 B is according to the embodiment of the present invention, before heteroatoms division, and the schema of another more detailed process of the embodiment of compound heteroatoms oxidising process;

Fig. 4 is according to the embodiment of the present invention, before heteroatoms division, and the schema of the more detailed process of the embodiment of compound heteroatoms oxidising process;

Fig. 5 is according to the embodiment of the present invention, before heteroatoms division, and the schema of another more detailed process of the embodiment of compound heteroatoms oxidising process.

Embodiment

Although the present invention contains many details, be construed as, variations and modifications can be carried out in the scope not exceeding technology described herein.The scope of this technology should never be interpreted as being only limitted to forming the order etc. of the quantity of component, the concentration of composition component and material thereof, shape, arranged opposite, application of temperature, combination of components, and should be interpreted as just example open.Description shown in this article and image are for exemplary object, and never should be interpreted as being only limitted to forming the order etc. of the quantity of component, connection, reactions steps and material thereof, shape, relative arrangement, reactions steps, and should be interpreted as being only and contribute to understanding and disclosing.Embodiment described herein relates to the oxidation of heteroatoms pollutent in hydrocarbon stream, this hydrocarbon stream comprises crude oil, refinery's intermediate product and refinery products, and these embodiments relate to the system and method for being removed from described hydrocarbon stream by described oxidized heteroatoms.

Unless otherwise indicated, the expression component quantity used in the present specification and claims, all numerical value of character such as molecular weight, reaction conditions etc. should be understood to, all can revise with " about " in all cases.Therefore, unless shown on the contrary, the numerical parameter described in following specification sheets and claims is approximation, the expected performance that can go for along with the present invention and changing.At least, do not attempt doctrine of equivalents to be applied to the scope limiting claim, each numerical parameter should at least according to the significant figure of record and by applying the routine technology of rounding off to explain.

Although the numerical range of wide region of the present invention's statement and parameter are approximations, the numerical value enumerated in the particular embodiment then as far as possible accurately record.But any numerical value is all inherently containing some certain errors, and this error is caused by the standard deviation certainly existed in each thermometrically value.

Use in this application, term " two-phase " refers to chemical system that be separated containing two kinds, obvious immiscible chemofacies.

Use in this application, term " promotion-corrosion viscosity breaker " refers to the reactor heating containing etching reagent and selectivity promotor, etching reagent and selectivity promotor and oxidized heteroatoms react, to remove desulfuration, Ni-V-Fe and other heteroatomss, increase api gravity, and reduce total acid value.

The term " contaminated hydrocarbon stream " used in the application is the mixture of the hydrocarbon containing heteroatoms composition." heteroatoms " comprises every other element in addition to carbon and hydrogen.

Oxidation can use at least one oxygenant, only carries out single step to realize, and selectively nitration mixture insoluble with at least one together uses with catalyzer.Reaction mixture, by for two-phase, comprises hydrocarbon ils phase and sour phase.The object of insoluble nitration mixture and oxidizer treatment is used to be part heteroatoms pollutent to remove from feed.Due to by insoluble nitration mixture and oxygenant oxidized, these heteroatomss will dissolve in acid mutually, then substantially be removed.

In another embodiment, oxidation also can be carried out two steps to realize; Initial oxidation uses at least one oxygenant, selectively together uses with catalyzer, and then use at least one oxygenant to carry out secondary oxidation, selectively nitration mixture insoluble with at least one together uses with catalyzer.Oxygenant in each step and selectable catalyzer may be the same or different.

Although other heteroatoms pollutents can be oxidized, initial oxidation step more selective oxidation contains the heteroatoms pollutent of sulphur and/or nitrogen.Secondary oxidation step is other heteroatoms pollutents of selective oxidation more, the pollutent such as containing metal heteroatom.By in the first oxidation using specific heteroatoms as target, for the second time chemical reaction efficiency can be improved, utilize another oxidizing reaction being oxidized more heteroatoms pollutent.

The temperature of carrying out oxidizing reaction can be about 20 DEG C to about 120 DEG C, and pressure is about 0.5 normal atmosphere extremely about 10 normal atmosphere, and duration of contact is about 2 minutes to about 180 minutes.The oxygenant used can be arbitrary oxygenant, selectively, when having catalyzer, oxidation is containing the heteroatoms in heteroatomic hydrocarbon feed, this oxygenant such as, but be not limited only to, hydrogen peroxide, peracetic acid, benzylic hydrogens superoxide, ethylbenzene hydroperoxide, cumyl hydrogen superoxide, clorox, oxygen, air etc., be more preferably this oxygenant at present and can not be oxidized in contaminated hydrocarbon feed not containing heteroatomic hydrocarbon.More preferably, catalyzer used herein can be any catalyzer, and this catalyzer can utilize oxygenant to be oxidized containing the heteroatoms in heteroatomic hydrocarbon feed.

Suitable catalyzer include but not limited to, and uses formula M _mo _m(OR) _nthe catalyst composition represented, wherein M is metal composite, and such as, such as, titanium or include but are not limited to any metal of rhenium, tungsten or other transition metal, these metals can cause separately or jointly the chemical conversion of sulphur class material as herein described.R is the carbon-containing group with at least 3 carbon atoms, wherein each R can be respectively the substituted alkyl group containing at least one OH group, the substituted cycloalkyl group containing at least one OH group, substituted cycloalkyl alkyl group containing at least one OH group, substituted heterocycle group containing at least one OH group, or the Heterocyclylalkyl containing at least one OH group.Subscript m and n are to the integer about between 8 respectively about 1.R can be replaced by halogen such as F, Cl, Br and I.In some embodiments, metal alcohol comprises two (glycerine) oxygen titanium (IV), and wherein M is Ti, m be 1, n is 2, and R is glycerine group.Litz etc. disclose in international publication number WO 2009/120238A1, other embodiment of metal alkoxide comprises two (ethylene glycol) oxygen titanium (IV), two (butantetraol) oxygen titanium (IV), and two (Sorbitol Powder) oxygen titanium (IV).

Other suitable catalyzer comprises, but be not limited only to, the catalyst composition prepared by Q-R-Q ' and two (polyvalent alcohol) oxygen titanium (IV) catalyst reaction, wherein Q and Q ' comprises isocyanate, acid anhydrides, sulfuryl halide, benzylic halides, carboxylic acid halide, phosphinylidyne acid halogenide (phosphoryl acid halide), silyl chloride or other chemical functional group that can react with-OH the pendant group of catalyzer all separately, and wherein R comprises linking group.International publication number as Litz etc. is disclosed in the international application of WO 2009/120238 A1, this R linking group is selected from: alkyl group (comprises alkyl group that is linear, side chain, saturated, undersaturated, ring-type and that replace, wherein heteroatoms can be contained in this alkyl group, such as oxygen, nitrogen, sulphur, silicon, phosphorus etc.), usually there is 1 to about 22 carbon atom, be preferably 1 to about 12 carbon atom, it is more preferably 1 to about 7 carbon atom, however, the number of carbon atom also can exceed these scopes, alkyl group (comprising substituted alkyl group), has about 6 to about 30 carbon atoms usually, preferably has about 6 to about 15 carbon atoms, and more preferably have about 6 to about 12 carbon atoms, however, carbonatoms also can exceed these scopes, aralkyl group (comprising the aralkyl group of replacement), has about 7 to about 30 carbon atoms usually, preferably has about 7 to about 15 carbon atoms, more preferably there are about 7 to about 12 carbon atoms, however, carbonatoms also can exceed these scopes, such as benzyl etc., alkylaryl group (comprising the alkylaryl group of replacement), usually there are about 7 to about 30 carbon atoms, preferably there are about 7 to about 15 carbon atoms, more preferably there are about 7 to about 12 carbon atoms, however, carbonatoms also can exceed these scopes, siliceous or phosphorus-containing groups, usually have about 1 to about 22 carbon atom, preferably have about 1 to about 12 carbon atom, more preferably have about 1 to about 7 carbon atom, however, carbonatoms also can exceed these scopes, polyalkylene oxide base (polyalkyleneoxy) group (comprising polyalkylene oxide base (polyalkyleneoxy) group of replacement), such as polyethyleneoxy (poly ethyleneoxy), polypropylene oxygen base (polypropyleneoxy), polybutene oxygen base (polybutyleneoxy) etc., usually there are about 3 to about 60 alkylene oxide group (alkyleneoxy) unit repeated, preferably there are 3 to about 30 alkylene oxide group (alkyleneoxy) unit repeated, more preferably have an appointment 3 to about 20 repeat alkylene oxide group (alkyleneoxy) unit, however, alkylene oxide group (alkyleneoxy) number of unit repeated also can exceed these scopes.

The insoluble nitration mixture used can be any acid being insoluble to hydrocarbon ils phase.The insoluble nitration mixture be applicable to can include but are not limited to carboxylic acid, sulfuric acid, hydrochloric acid and composition thereof, and its water or do not have with different amount is as thinner.The carboxylic acid be applicable to can include but are not limited to formic acid, acetic acid, propionic acid, butyric acid, lactic acid, phenylformic acid etc. and composition thereof, and its water or do not have with different amount is as thinner.

After oxidizing reaction, the solvent used when extracting and containing heteroatomic hydrocarbon stream (such as, in liquid-liquid extractor) can be that solvability in oil is lower, but any solvent that solvability is higher in containing oxidized heteroatomic hydrocarbon, include but are not limited to acetone, methyl alcohol, ethyl lactate, N-N-methyl 2-pyrrolidone N-, N,N-DIMETHYLACETAMIDE, dimethyl formamide, gamma-butyrolactone, methyl-sulphoxide, propylene carbonate, acetonitrile, acetic acid, sulfuric acid, sulfur dioxide liquid etc., heteroatoms can extract from containing heteroatomic hydrocarbon stream by this solvent, obtained substantially not containing heteroatomic hydrocarbon product.

Etching reagent of the present invention can be any compound presenting fundamental property, includes but are not limited to metal hydroxides and metallic sulfide, and such as alkali metal hydroxide and alkali metalsulphide, include but are not limited to LiOH, NaOH, KOH and Na ₂s; Alkaline earth metal hydroxides, such as Ca (OH) ₂, Mg (OH) ₂, and Ba (OH); Carbonate, such as alkaline carbonate, include but are not limited to Na ₂cO ₃, K ₂cO ₃; Alkaline earth metal carbonate, such as CaCO ₃, MgCO ₃and BaCO ₃; Phosphoric acid salt, includes but are not limited to alkali metal phosphate, such as trisodium phosphate, potassium pyrophosphate, Tri sodium Phosphate and tri-potassium phosphate; And alkali earth metal phosphate, such as Calcium Pyrophosphate, magnesium pyrophosphate, barium pyrophosphate, calcium triphosphate, triphosphoric acid magnesium and triphosphoric acid barium; Silicate, such as alkalimetal silicate, such as water glass and potassium silicate, and alkaline earth metal silicate, such as Calucium Silicate powder, Magnesium Silicate q-agent and barium silicate, with general formula R-E ⁿm ^mq ^m-1the organo-alkali compound of expressing, wherein R is that hydrogen or organic compound (it can be further substituted) include but are not limited to straight chained alkyl, branched-chain alkyl and cycloalkyl; Straight-chain alkenyl, branched-chain alkenyl and cycloalkenyl group; And aromatic base or multiring aromatic.Further, in substituting group, R is organism, can comprise hydroxide radicals, carbonyl, aldehyde radical, ether, carboxylic acid and carboxylic acid group, phenol or phenates base, alkoxide group, amido, imido grpup, cyano group, thiol group or mercaptan alkali, thioether group, disulfide group, sulfate and phosphate.E ^n-represent atom (wherein n=-1 ,-2 ,-3 ,-4 etc.) such as oxygen, sulphur, selenium, tellurium, nitrogen, phosphorus and the carbon with negative charge; M ^mfor arbitrary positively charged ion (m=+1 ,+2 ,+3 ,+4 etc.), such as metal ion, includes but are not limited to basic metal, such as Li, Na and K; Alkaline-earth metal, such as Mg and Ca; And transition metal, such as Zn and Cu.Work as m>+1, Q can and E ⁿ-R is identical, or can be the atom with negatron, such as Br ^-, Cl ^-, I, or can be and support positive ion M ^mthe anionic group of charge balance, includes but are not limited to oxyhydroxide, prussiate, cyanate and carboxylate salt.

The embodiment of side chain or branched-chain alkyl can comprise methyl, ethyl, normal-butyl (n-butyl), isobutyl-(i-butyl), sec-butyl (sec-butyl), the tertiary butyl (t-butyl), octyl group, 2-ethylhexyl and octadecyl.The embodiment of the thiazolinyl of straight or branched can comprise vinyl, propenyl, allyl group and butenyl.The embodiment of cycloalkyl and cycloalkenyl group can comprise cyclohexyl, cyclopentyl and tetrahydrobenzene.The embodiment of aromatic base or multiring aromatic can comprise aryl, such as phenyl, naphthyl, anthracene; Aralkyl, such as benzyl and styroyl; Alkylaryl, such as tolyl, ethylbenzene, nonylphenol, first naphthyl and ethylnaphthalene base.

Based on reaction conversion ratio and selectivity, preferred etching reagent compound is alkali metal hydroxide and alkali metalsulphide, such as NaOH, KOH, Na ₂s and/or its mixture.

In one embodiment of the invention, this etching reagent can be molten state.At present preferred molten state etching reagent includes but not limited to the mixture of fusing point lower than the inorganic hydroxide of 350 DEG C, such as, such as molecular fraction be 51% NaOH and molecular fraction be the eutectic mixture of the KOH of 49%, it is 170 DEG C of fusings.

In another embodiment of the present invention, this etching reagent can load on inorganic carrier, oxide compound that is that this inorganic carrier includes but not limited to inertia or activity, such as, the carrier of such as porous, such as talcum or inorganic oxide.

Suitable inorganic oxide includes, but not limited to the oxide compound of element of IB race in the periodic table of elements, II-A and II-B race, III-A and II-B race, IV-A and IV-B race, V-A and V-B race, VI-B race.Oxide compound, as the preferred embodiment of carrier, comprises the mixed oxide of cupric oxide, silicon-dioxide, aluminum oxide and/or copper, silicon and aluminium.Can be used alone other suitable inorganic oxide, or by other suitable inorganic oxide and above-mentioned preferred oxide carrier used in combination, this other suitable inorganic oxide can be, such as MgO, ZrO ₂, TiO ₂, CaO and/or its mixture.

The specific surface area of the solid support material of this use can be 10m ²/ g to 1000m ²/ g, pore volume is 0.1ml/g to 5ml/g, and median size is 0.1 to 10cm.Preferably, the specific surface area of carrier is 0.5 to 500m ²/ g, pore volume is 0.5ml/g to 3.5ml/g, and median size is about 0.5cm to 3cm.More preferably, the specific surface area of carrier is 200m ²/ g to 400m ²/ g, and pore volume is 0.8ml/g to 3.0ml/g.

Selectivity promotor of the present invention can be any organic compound with at least one acid proton.Usually, pKa (acidity quotient) value measured in the DMSO (dimethyl sulfoxide (DMSO)) of selectivity promotor from the scope of about 9 to 32, preferably from the scope of about 18 to 32.The embodiment of selectivity promotor includes but are not limited to, the organic compound of hydroxy-functional; There is the substituent straight chain of at least one H, side chain or cyclammonium base; And/or its mixture.Selectivity promotor also can comprise crown ether.

The organic compound of the hydroxy-functional be applicable to includes but are not limited to: (i) linear alcohols, branched alkanol or cycloalkanol (it can be further substituted), such as methyl alcohol, ethanol, Virahol, ethylhexanol, hexalin, thanomin, diethanolamine, trolamine, monomethyl thanomin and dimethylethanolamine; Comprise glycol, such as ethylene glycol, propylene glycol, 1,3-PD and 1,2-cyclohexanediol; Polyvalent alcohol, such as glycerol, erythritol, Xylitol, sorbyl alcohol etc.; Monose, such as glucose, fructose, semi-lactosi etc.; Disaccharides, such as sucrose, lactose and maltose; Polysaccharide, such as starch, Mierocrystalline cellulose, glycogen, chitin, wood chip and wood shavings; (ii) straight-chain alkenyl alcohol, branched-chain alkenyl alcohol or cycloalkenyl group alcohol (it can be further substituted), such as vinyl alcohol, vinyl carbinol; (iii) aryl alcohol and aralkyl alcohol (it can be further substituted), such as phenol and phenylcarbinol; (iv) polyaromatic alcohol and many cyclophanes alkyl alcohol (it can be further substituted), such as naphthols and naphthane alcohol; And (v) ammonium salt, such as choline and benzyl TMA (TriMethylAmine) oxyhydroxide (benzyltrimethylammonium hydroxide).

The embodiment of straight chained alkyl or branched-chain alkyl can comprise: methyl, ethyl, normal-butyl, sec-butyl, the tertiary butyl, octyl group, 2-ethylhexyl and octadecyl.The embodiment of the thiazolinyl of straight or branched can comprise vinyl, propenyl, allyl group and butenyl.The embodiment of cycloalkyl and cycloalkenyl group can comprise cyclohexyl and cyclopentyl.The embodiment of aromatic base, aralkyl or multiring aromatic can comprise aryl, such as phenyl, Lai Ji, anthracene; Aralkyl, such as benzyl and styroyl; Alkylaryl, such as tolyl, ethylbenzene, nonylphenol, first naphthyl and ethylnaphthalene base.

The amine be applicable to includes but are not limited to has the substituent straight chain amine of at least one H, chain amine and cyclammonium, it can be further substituted, include but are not limited to monosubstituted amine or bis substituted amine, such as methylamine, ethamine, 2-ethylhexyl, piperazine, 1，2-diaminoethane and/or its mixture.

The crown ether be applicable to, it can be further substituted, and includes but are not limited to hexaoxacyclooctadecane-6-6,15-crown ether-5 etc.; And/or its mixture.

Based on reaction conversion ratio and selectivity, preferred selectivity promotor is ethylene glycol, propylene glycol, trolamine and/or its mixture.

In one embodiment of this invention, at least one etching reagent and at least one selectivity promotor can be different components.In another embodiment of the invention, at least one etching reagent and at least one selectivity promotor can be identical component.When at least one etching reagent and at least one selectivity promotor are identical component, they can be considered to etch selectivities promotor.In addition, the etch selectivities promotor be applicable to can have the performance of at least one etching reagent and at least one selectivity promotor.That is, the combination of etching reagent and selectivity promotor can be reacted (in reaction process or before) and be formed etch selectivities promotor, and it has the performance of etching reagent and selectivity promotor.

Etch selectivities promotor can be reacted with containing oxidized heteroatomic compound, such as dibenzothiophene, sulfoxide, dibenzothiophene sulphone, and/or its mixture, to generate substantially unoxidized hydrocarbon product, such as biphenyl.The nonlimiting examples of etch selectivities promotor includes but are not limited to sodium ascorbate, SODIUM ISOVITAMIN C, Sunmorl N 60S, 4-hydroxyphenyl ethylene glycol, starch or cellulosic sodium salt, the sodium salt of starch or cellulosic sylvite, chitin or chitosan, the sylvite of chitin or chitosan, hydroxy acid sodium, Glycerose sodium salt, 1-sulphur-β-D-Glucose sodium salt and/or its mixture.

Such as, etching reagent (such as sodium hydroxide and/or potassium hydroxide) and selectivity promotor (such as ethylene glycol) can reacting when heteroatomic hydrocarbon stream contacts with containing being oxidized or reacting before contact, form water and etch selectivities promotor, the sodium salt of such as ethylene glycol or sylvite.Usually, in order to transformation efficiency and selectivity, it is excessive that selectivity promotor hydroxyl and the cationic molar ratio of etching reagent are preferably.

Promote-corrode that the reaction conditions of viscosity breaker is: temperature range is about 150 DEG C to about 350 DEG C, and pressure is about 0 to about 2000 pound/square inch (psig), and duration of contact is about 2 minutes to about 180 minutes.Be not restricted to any special theory, think that this reaction mechanism comprises solvolysis reaction, the alcoholysis especially when selectivity promotor is alcohols, the ammonia solution when selectivity promotor is amine; If do not have the selectivity promotor of the application, this reaction mechanism may relate to hydrolytic action, and this can cause forming fully oxidized product undesirably.

Usually, the molar ratio of etching reagent and selectivity promotor is in the scope of about 10:1 to about 1:10, the molar ratio of etching reagent and selectivity promotor is preferably in the scope of about 3:1 to about 1:3, and the molar ratio of etching reagent and selectivity promotor is more preferably in the scope of about 2:1 to about 1:2.

Usually, total amount and the heteroatomic molar ratio contained in heteroatomic hydrocarbon feed oil of etching reagent and selectivity promotor are in the scope of about 100:1 to about 1:1, etching reagent and selectivity promotor be preferably in the scope of about 10:1 to about 1:1 containing the heteroatomic molar ratio in heteroatomic hydrocarbon feed oil, etching reagent and selectivity promotor are more preferably in the scope of about 3:1 to about 1:1 with containing the heteroatomic molar ratio in heteroatomic hydrocarbon feed oil.

By gravity by heavy etching reagent phase and light separation of oil.Other suitable methods include but are not limited to the solvent extraction of etching reagent phase or oil phase, as by with water flushing, centrifugation, distillation, cyclonic separation, thin film separation and composition thereof.According to currently known methods, those skilled in the art can remove etching reagent and the selectivity promotor of trace.

Because heteroatoms pollutent is removed from containing heteroatomic hydrocarbon stream, compared with untreated contaminated stream, light oil phase product has lower density and viscosity.The density of heavy etching reagent phase is usually from the scope of about 1.0 to about 3.0g/mL, and the density of light product oil phase is usually from the scope of about 0.7 to about 1.1g/mL.

As shown in Figure 2, can combine with oxygenant 11 containing heteroatomic hydrocarbon feed 10, and carry out oxidising process in oxidant vessel 12, to meet the existing and following environmental standard.This oxidant vessel 12 is optionally containing catalyzer or promotor (not shown).

Make after hydrocarbon stream is in oxidizing condition in oxidant vessel 12, is oxidized heteroatomic compound (such as, dibenzothiophene being oxidized to sulfone class) at least partially thus, the first intermediate flow 13 can be produced.This first intermediate flow 13 can be combined with oxygenant 7 and insoluble nitration mixture, oxidising process is carried out in acid treatment reactor 8, be oxidized the heteroatomic compound (such as oxidized metal porphyrin is to generate porphyrin and metal-salt) of another part thus, produce intermediate flow 9 and metallic acidic by-products stream 79.This intermediate flow can react with etching reagent (such as, sodium hydroxide, hydrogen-oxygen acid potassium and eutectic mixture etc. thereof) and selectivity promotor 24, to produce the intermediate flow 16 of two-phase in reactor 14.

Intermediate flow 16 can be transferred to product separation device 18, by its can from light mutually reclaim and substantially do not contain heteroatomic hydrocarbon product 20.As understood by those skilled in the art, close phase 21 containing selective promotor and etching reagent and heteroatoms by product can be transferred to returnable 22, in this returnable 22, this selectivity promotor recyclable and etching reagent 24, and recycle in reactor 14, and recovery zone can be delivered to process further by containing heteroatomic by product 26.

Illustrated in Fig. 3 A, in embodiment more specifically, can combine with hydroperoxide 32 in catalytic oxidizer 34 containing heteroatomic hydrocarbon feed 30, be oxidized heteroatoms thus, produce intermediate flow 36.Intermediate flow 36 can be transported to separation of by-products device 38, by its this hydroperoxide by product recyclable, and can in catalytic oxidizer 34 cycling and reutilization (as understood by those skilled in the art), produce intermediate flow 39.Intermediate flow 39 can react with oxygenant 7 and insoluble nitration mixture feed 77 in acid treatment post 71, produces intermediate flow 73 from hydrocarbon phase, from acid mutually, generate intermediate flow 75.Intermediate flow 75 can be supplied to solvent recovery unit 81, and from wherein recyclable sour 77, and generate metallic byproduct stream 79, this acid 77 is circulated to acid treatment post 71 and reuses.

Intermediate flow 73 can react with selectivity promotor and etching reagent feed 42 in viscosity breaker 40 containing promoting-corroding, two phase flow 44 in the middle of generating, this middle two phase flow 44 can be separated in product separation device 46, substantially not contain heteroatomic hydrocarbon product 48 from light middle generation mutually.Those skilled in the art are known, and the close phase 49 in product separation device 46 is transferred to heteroatoms separation of by-products device 50, from wherein reclaiming containing heteroatomic byproduct stream 52, selectivity promotor and etching reagent feed 42 respectively.

As shown in Figure 3 B, in another embodiment, can combine with hydroperoxide 32 containing heteroatomic hydrocarbon feed 30, and in catalytic oxidizer 34 with catalyst reaction, produce intermediate flow 36, it can react with oxygenant 7 and insoluble nitration mixture feed 77 in acid treatment post 71, generates intermediate flow 73, and generate intermediate flow 75 mutually from acid from hydrocarbon phase.Intermediate flow 75 can be supplied to solvent recovery unit 81, and from wherein recyclable sour 77, and generate metallic byproduct stream 79, this acid 77 is circulated in acid treatment post 71 to be reused.

Intermediate flow 73 is transferred to promotion-corrosion viscosity breaker 40, and wherein, this intermediate flow 73 reacts with selectivity promotor and etching reagent feed 42, produces the second intermediate flow 62 of two-phase.Intermediate flow 62 is transferred to product separation device 38, from wherein substantially not can be used as gently remove mutually containing heteroatomic hydrocarbon product stream 48, is then transported to storage or for commercial use.Those skilled in the art are known, close phase 64 can be separated into two kinds of streams by separation of by-products device 54: containing heteroatomic byproduct stream 52 (its can be transported to store or for commercial use) and byproduct mixture stream 66, and this byproduct mixture stream 66 is containing for reclaiming and the selectivity promotor of recycle, etching reagent and hydroperoxide by product.

As shown in Figure 4, in another embodiment, can mix mutually with hydroperoxide feed 32 containing heteroatomic hydrocarbon feed 30, and react with catalyzer or promotor (not shown) in catalytic oxidizer 34, generate intermediate flow 36.Intermediate flow 36 is transferred to separation of by-products device 38, by wherein separable hydroperoxide by product 37, generates intermediate flow 70.Solvent 78 extract stream 70 can be passed through in product separation device 46 (such as, liquid-liquid extraction post), can extract thus substantially not containing heteroatomic hydrocarbon product 72, obtain the 3rd intermediate flow 74.Stream 74 can be delivered to solvent recuperation 76, by its solvent-recoverable 78, and is circulated to product separator 46, generates intermediate flow 80.Intermediate flow 80 can react with oxygenant 7 and insoluble nitration mixture feed 77 in acid treatment post 71, generates intermediate flow 73, generate intermediate flow 75 mutually from acid from hydrocarbon phase.Intermediate flow 73 can be supplied to solvent recovery unit 81, and from wherein recyclable sour 77, and generate metallic byproduct stream 79, this acid 77 circulates and heavily uses in acid treatment post 71.

Intermediate flow 73 can process in the promotion-corrosion viscosity breaker 40 containing selective promotor and etching reagent feed 42, generates two-phase intermediate flow 82.Can in product separation device 84 two-phase of separated flow 82: light by mutually 48 and close phase 86.Light phase 48 can comprise substantially not containing heteroatomic hydrocarbon product, and it can store or for commercial use.Those skilled in the art are known, close phase 86 can be transferred to heteroatoms separation of by-products device 88, thus can by containing heteroatomic byproduct stream 52 from being separated containing selective promotor and the stream 42 of etching reagent of generating, this selectivity promotor and etching reagent can recovery and recycling in promotion-corrosion viscosity breaker 40.

As shown in Figure 5, in another embodiment, can be delivered to catalytic oxidizer 34 containing heteroatomic hydrocarbon feed 30, wherein, this hydrocarbon feed 30 can react with the catalyst stream 90 in catalytic oxidizer 34, generates intermediate flow 92.Stream 92 is transferred to catalyst separator 94, and intermediate flow 70 can be separated in this catalyst separator 94 with discarded catalyst stream 96.Stream 96 can be delivered to catalyst regenerator 98, is regenerated by oxygenant feed 100, generates catalyst stream 90 and oxygenant byproduct stream 102.It will be appreciated by those skilled in the art that oxygenant byproduct stream 102 optionally reclaims, circulates and reuses.In product separation device 46 (such as liquid-liquid extraction post), by solvent 78 extract stream 70, substantially can will not extract containing heteroatomic hydrocarbon product 72 thus, generate the 3rd intermediates 74.3rd intermediates 74 can be delivered to solvent recuperation 76, this solvent of recycle by this solvent recuperation 76 solvent-recoverable 78 and in product separation device 46, generate intermediate flow 80.Intermediate flow 80 can react with oxygenant 7 and insoluble nitration mixture feed 77 in acid treatment post 71, generates intermediate flow 73, generate intermediate flow 75 mutually from acid from hydrocarbon phase.Intermediate flow 75 can be supplied to solvent recovery unit 81, and wherein recyclable sour 77, and generate metallic byproduct stream 79, this acid 77 circulates and heavily uses in acid treatment post 71.

Stream 73 can process in the promotion-corrosion viscosity breaker 40 containing selective promotor and etching reagent feed 42, generates the intermediate flow 82 of two-phase.The two-phase that can flow 82 in product separation device 84 is separated: light phase 48 and close phase 86.Light phase 48 can containing substantially containing heteroatomic hydrocarbon product, and this product can be transported to and to store or for commercial use.Those skilled in the art should know, this close phase 86 can be transferred to heteroatoms separation of by-products device 88, thus separable go out containing heteroatomic byproduct stream 52, obtain stream 42, stream that this obtains 42 is containing selective promotor and etching reagent, recyclable and circulate in promotion-corrosion viscosity breaker 40 and heavily use.

Following non-limiting examples has set forth some aspect of the present invention.

Embodiment

Embodiment 1

The polymerization titanyl catalyzer of preparation pellet

Prepare comonomer (such as, 4, the two acid anhydride (BPADA) of 4 '-dihydroxyphenyl propane) dimethyl sulfoxide (DMSO) (DMSO) solution, and by itself and titanyl compound (such as, two (glycerine) oxygen titanium (IV)) DMSO solution combine, stir about 4 hours at 70 DEG C, generates copolymer solution.Then, this solution is cooled to room temperature, by the excessive acetone precipitation of this polymer product.By collected by vacuum filtration also this polymeric precipitation thing dry.The productive rate of the polymeric oxygen Ti-base catalyst of deposition is greater than 90%.

Tackiness agent is prepared in solid mixer or agitator the mixture of selectable inertia weighting material (silicon or aluminium) and polymeric oxygen Ti-base catalyst.The mixture of this mixing is extruded by compression or makes coccoid, forms the homogeneous catalyst pellet that hardness test intensity is preferably greater than 2kp.

Embodiment 2

From the light atmospheric oil polluted by heteroatoms, catalysis removes heteroatoms constantly

At about 85 DEG C, by the light atmospheric oil (LAGO) (sulfur-bearing 3.45%) of straight run and cumyl hydrogen superoxide, (cumyl content is 30%, during with reaction of Salmon-Saxl in LAGO feed, molar equivalent is 2.1) mixing is 1.0hr with liquid hourly space velocity ^-1be delivered to the fixed-bed reactor containing pellet titanyl catalyzer, generate the first intermediate flow, this pellet titanyl catalyzer obtains according to embodiment 1.This first intermediate flow is supplied to the reactor that temperature is the heating of 50 DEG C, is combined with the feed streams containing acetic acid, hydrogen peroxide and remaining cumene hydroperoxide in the reactor, to generate two-phase mixture, then flows out from reactor.This two-phase mixture passes through gravity separation, generate the second intermediate flow of light phase and the byproduct stream of heavy phase, second intermediate flow of this light phase comprises the light atmospheric oil that heteroatoms fully reduces, and the byproduct stream of this heavy phase consists essentially of acetic acid, oxide compound and containing heteroatomic salt.This second intermediate flow vacuum distilling under-25 inches of mercury, removed from heavy second intermediate flow by lower boiling distillment and reclaim, this distillment comprises cumene, cumic alcohol, alpha-methyl styrene, Ethenylbenzene and remaining acetic acid.This heavy second intermediate flow comprises the light atmospheric oil with oxidized heteroatomic compound substantially.Then this second is supplied to the reactor of heating, and wherein (liquid residence time of combination is 1.0hr with the feed streams comprising etching reagent and ethylene glycol ^-1) combine, to generate the mixture of two-phase, then flow out from reactor.The mixture of this two-phase generates light phase product and heavy phase byproduct stream by gravity separation subsequently, and this light phase product comprises substantially not containing heteroatomic LAGO, and this heavy phase byproduct stream substantially comprises etching reagent, ethylene glycol and contains heteroatomic salt.The element of measure sample is formed, and compares with LAGO feed synthetics, and the sulphur removed from light phase product is greater than 50%, and the nitrogen of removal is greater than 50%, and the vanadium of removal is greater than 50%, and the nickel of removal is greater than 50%, and the iron removed is greater than 50%.According to known method, heavy phase by product is processed further, to reclaim and etching reagent in recycle heteroatoms by product and ethylene glycol.

Be to set forth and describe to the object of the above-mentioned explanation of embodiment of the present invention, and be not intended to limit or limit the present invention to disclosed specific form, apparently, can numerous modifications and variations be carried out.For a person skilled in the art, these modifications and variations are all obvious, and within the scope being included in foregoing invention.

Claims (20)

1. carry out the method for upgrading containing heteroatoms hydrocarbon stream by removing heteroatoms pollutent, the method comprises:

To contact with insoluble nitration mixture with oxygenant containing heteroatomic hydrocarbon feed;

Contact containing oxidized heteroatomic hydrocarbon feed with at least one selectivity promotor with at least one etching reagent, described at least one selectivity promotor comprises the organic compound with at least one acid proton; And

Heteroatoms pollutent is removed from containing heteroatomic hydrocarbon feed.

2. method according to claim 1, is characterized in that, described at least one etching reagent and described at least one selectivity promotor are different components.

3. method according to claim 1, is characterized in that, the scope of the acidity quotient value that described selectivity promotor dimethyl sulfoxide (DMSO) is measured is about 9 to about 32.

4. method according to claim 1, is characterized in that, described at least one selectivity promotor also comprises crown ether.

5. method according to claim 1, is characterized in that, described at least one selectivity promotor is selected from the organic compound of hydroxy-functional; There is the substituent straight chain amine of at least one hydrogen, chain amine or cyclammonium; And/or its mixture.

6. method according to claim 5, is characterized in that, at least one selectivity promotor described is the organic compound of hydroxy-functional.

7. method according to claim 6, is characterized in that, the organic compound of described hydroxy-functional is selected from ethylene glycol, propylene glycol, trolamine and/or its mixture.

8. method according to claim 7, is characterized in that, the organic compound of described hydroxy-functional is ethylene glycol.

9. method according to claim 1, is characterized in that, described at least one etching reagent is selected from the inorganic oxide of the element of IA race and IIA race and inorganic sulphide, the inorganic hydroxide of IA race and IIA race element and/or its mixture.

10. method according to claim 9, is characterized in that, described at least one etching reagent is selected from NaOH, KOH, Na ₂s and/or its mixture.

11. methods according to claim 1, is characterized in that, described at least one etching reagent and described at least one selectivity promotor are identical component.

12. methods according to claim 11, is characterized in that, described identical component is formed in reaction process.

13. methods according to claim 11, is characterized in that, described at least one etching reagent is the oxyhydroxide of IA race or IIA race, and described at least one selectivity promotor is ethylene glycol.

14. methods according to claim 11, is characterized in that, described identical component be formed at described to contact with at least one selectivity promotor containing oxidized heteroatomic hydrocarbon feed and at least one etching reagent before.

15. methods according to claim 1, is characterized in that, are removed by heteroatoms pollutent by gravity from containing heteroatomic hydrocarbon feed.

16. methods according to claim 1, is characterized in that, by carrying out solvent-extracted mode with water, are removed by described heteroatoms pollutent from described containing heteroatomic hydrocarbon feed.

17. methods according to claim 1, is characterized in that, the molar ratio of etching reagent and selectivity promotor is in the scope of about 10:1 to about 1:10.

18. methods according to claim 1, is characterized in that, the total amount of etching reagent and selectivity promotor and described containing the heteroatomic molar ratio in heteroatomic hydrocarbon feed in the scope of about 100:1 to about 1:1.

19. carry out the method for upgrading containing heteroatomic hydrocarbon feed by removing heteroatoms pollutent, described method comprises and is oxidized to sulfone by containing the dibenzothiophene in heteroatomic hydrocarbon feed, by sulfone and insoluble nitration mixture and oxidising agent under oxidation two-phase condition, to remove heteroatoms pollutent at least partially, then by sulfone and etching reagent and selectivity booster response, be separated and be substantially used as fuel containing heteroatomic hydrocarbon product.

20. methods according to claim 19, is characterized in that, not containing the density of heteroatomic hydrocarbon product about 0.7 to about between 1.1g/mL.