CN109963827A - The method for preparing paraxylene by the methylation of toluene and/or benzene - Google Patents
The method for preparing paraxylene by the methylation of toluene and/or benzene Download PDFInfo
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Abstract
A method of paraxylene is produced by the catalytic alkylation of benzene and/or toluene and methanol.In prior art approaches, usually by water and the co-implanted utilization rate to improve methanol of methanol, increase the quantity of methyl alcohol reacted with benzene and/or toluene, and reduces and resolve into unwanted carbon monoxide, carbon dioxide or water react the quantity of methyl alcohol for generating unwanted light olefin gas with its own.Without using the methanol and the water that feeds jointly of purifying as taught in the art, the total amount fed based on water and methanol, contain at least 5wt%, such as 5 may be used as alkylating agent to the crude or unpurified methanol of 35wt% water, if not the needs for completely, at least partly reducing total injection water.
Description
Priority claim
This application claims the U.S. Provisional Patent Application for the patent application serial numbers 62/430,021 submitted on December 5th, 2016 and
The priority and right for the EP 17150624.9 that on January 9th, 2017 submits, respective content are incorporated herein by reference.
Technical field
Disclosure of this application is related to the method that unpurified methanol is used in the method for production gasoline and aromatic hydrocarbons.More
Specifically, by the alkylation of benzene and/or toluene and methanol, unpurified methanol is used as the methylation in paraxylene preparation
Agent.
Background technique
In xylene isomer, paraxylene has special value, right because it can be used for manufacturing terephthalic acid (TPA)
Phthalic acid is the intermediate in synthetic fibers and resin manufacture.Currently, paraxylene (is urged by the hydrotreating of naphtha
Change and reform), the steam cracking and toluene disproportionation of naphtha or gas oil carry out commodity production.
One problem of most of existing methods for producing dimethylbenzene is that they are generated adjacent (o)-, (m)-and right
(p)-dimethylbenzene thermodynamical equilibrium mixture, wherein para-xylene concentration is typically only about 24wt%.Therefore, from this mixing
Separating paraxylene tends to that oversubscription is needed to evaporate and multi-stage refrigerating step in object.These processes are related to high operation and capital cost,
And only generate limited yield.Accordingly, it has been required to which providing has highly selective method for paraxylene preparation.
It is well known that the alkylation by toluene and/or benzene and methanol prepares dimethylbenzene, especially with zeolite catalyst
Selectively prepare paraxylene (PX) product.See, e.g., Patent No. 4,002,698；4356338；4423266；
5675047；5804690；5939597；6028238；6046372；6048816；6156949；6423879；6504072；
6506954；6538167；With 6,642,426 United States Patent (USP).Term " Selectivity for paraxylene ", " para-selectivity " etc. refer to
The yield of paraxylene is greater than to be measured present in xylene different structure mixture under thermodynamical equilibrium, in routinely preparation temperature
It is about 24mol% under degree.Economic Importance due to paraxylene relative to meta-xylene and ortho-xylene is paid high attention to
The selectivity of paraxylene.Although every kind of xylene isomer has important and well-known final use, at present to two
Toluene is most economic value.
In the method, usually in the presence of suitable catalysts with methanol by toluene and/or benzene alkylation, in figure
Dimethylbenzene is formed in the reactor of the system schematically illustrated, wherein the charging comprising reactant enters fluidized bed by pipeline 1
Reactor 11 and effluent including product is discharged by pipeline 5 and catalyst passes through conduit 2,3 and 4 in fluidized bed respectively
Reactor 11 recycles between device 12 (its from stripping fluid in catalyst) and catalyst regenerator 13.Usually by water and toluene
It is fed jointly with methanol so that toluene coking and methanol selfdecomposition in feeding line minimize.Other side reactions include being formed gently
Matter alkene, light paraffinic hydrocarbon such as convert other xylene isomers for paraxylene or compared with the reaction of heavy aromatics.
It is expected that continuing to improve this method and saving energy and cost.
Summary of the invention
Embodiment disclosed in the present application, which is provided, to be prepared by the catalytic alkylation of benzene and/or toluene and methanol to diformazan
The method of benzene.In prior art approaches, usually by water and the co-implanted utilization rate to improve methanol of methanol, increase and benzene
And/or the quantity of methyl alcohol of toluene reaction, and reduce and resolve into unwanted carbon monoxide, carbon dioxide or water, or is anti-with its own
The quantity of methyl alcohol of unwanted light olefin gas should be generated.It is not the methanol and be total to that use as taught in the art purifies
With the water of charging, but use the total amount fed based on water and methanol contain at least 5wt%, such as 5 to 35wt% water it is crude
Or alkylating agent is made in unpurified methanol charging, reduces the need at least partly injecting water altogether (if reducing whole)
It wants.It is therefore understood that not additional water injects altogether together with unpurified methanol at least some embodiments.Make
It is beneficial with the non-purification of methanol containing at least 5wt% water, because it reduces cost relevant to purchase raw material and saves
The fund and energy of methanol production step.
In one embodiment, in the presence of alkylation reactor, in alkylation reactor, under alkylating conditions
Make toluene and/or benzene and alkylating agent, to generate the alkylation effluent for including paraxylene.Based on non-purification of methanol
Weight, the non-purification of methanol containing at least 5wt% water are used as alkylating agent.Then it can recycle from alkylation effluent to two
Toluene.
Can also be used for the other methods of production gasoline and aromatic hydrocarbons using unpurified methanol, for example, methanol to gasoline method or
Methanol is to aromatic hydrocarbons method.
Detailed description of the invention
The figure is the schematic diagram of reactor assembly, which includes reactor and regenerator and known in the art
Some relevant auxiliary devices and conveyance conduit.
Specific embodiment
Disclosed herein is the methods that the catalytic alkylation by benzene and/or toluene and methanol prepares paraxylene.Existing
In technical method, usually water and methanol is injected to improve the utilization rate of methanol altogether, increase the methanol reacted with benzene and/or toluene
Amount, and reduce to resolve into unwanted carbon monoxide, carbon dioxide or water or react with its own and generate unwanted lightweight alkene
The quantity of methyl alcohol of appropriate hydrocarbon gas.The methanol of use purifying not instead of not as taught in the art and the water fed jointly, use
Total amount based on water and methanol contain at least 5wt%, such as 5 to 35wt% water crude or unpurified methanol charging be used as alkane
Base agent reduces the needs at least partly injecting water altogether (if not complete reduce).It will thus be appreciated that extremely
In few some embodiments, not additional water injects altogether together with unpurified methanol.Using containing at least 5wt% water not
Purification of methanol is beneficial because it reduce to the relevant cost of purchase raw material and save methanol production step fund and
Energy.
As used herein, " crude carbinol " or " unpurified methanol " refers to not through at least one of methyl alcohol product installation
Purify the methanol of fractionating column processing.The practical composition of unpurified methanol will be according to production process and the purification step carried out
(if any) change." crude carbinol " and " unpurified methanol " is used interchangeably herein.
Any aromatic raw material comprising benzene and/or toluene can be used in alkylation used herein, but generally preferably
Aromatic feed contains at least 90wt%, the especially at least toluene of 99wt%.This method can be fixed in one or more, mobile
Or it is carried out in fluidized-bed reactor, and use any catalyst system known in the art.
In specific embodiments, catalyst used in alkylation is usually porous crystalline material, and
It is to work as to measure at 120 DEG C of temperature and 2,60 support of 2- dimethylbutane pressure (8kPa) in one preferred embodiment
When have about 0.1-15sec-12,2- dimethylbutane diffusion parameter porous crystalline material.
As used herein, the diffusion parameter of specific porous crystalline material is defined as D/r2×106, wherein D is diffusion coefficient
(cm2/ sec) and r be crystal radius (cm).Diffusion parameter can show that condition assumes that planar sheet model from absorption measurement
Diffusion process is described.Therefore, Q is loaded for given adsorbate, wherein QeqIt is the numerical value Q/Q of equilibrium adsorption object loadeqWith
(Dt/r2)1/2Mathematically related, wherein t is the time (second) needed for reaching adsorbate load Q.The figure of planar sheet model
Solution is by J.Crank in " The Mathematics of Diffusion ", Oxford University Press, Ely
House, London disclose in 1967.
Porous crystalline material is preferably the aluminosilicate zeolite of intermediate pore size.It is about 5 that mesopore zeolite, which is normally defined aperture,
To about 7 angstroms of zeolite, so that zeolite freely binding molecule such as n-hexane, 3- methylpentane, benzene and paraxylene.Mesoporous boiling
Another Common definitions of stone are related to restricted index test, which is described in United States Patent (USP) US4,016,218, this is specially
Benefit is hereby incorporated by reference.In the case, mesopore zeolite has the restricted index of about 1-12, such as surveys on individual zeolite
Amount is such without introducing oxide modifier, and will be before diffusivity of any steam treatment to adjust catalyst.It removes
Except the aluminosilicate zeolite of intermediate pore size, other mesoporous acid metal silicates, such as silicoaluminophosphate (SAPO), it can use
In the method for the present invention.
The specific example of suitable mesopore zeolite includes ZSM-5, ZSM-11, ZSM-12, ZSM-22, ZSM-23, ZSM-35
And ZSM-48, particularly preferably ZSM-5 and ZSM-11.In one embodiment, zeolite used is ZSM-5, is had at least
250 silica and the molar ratio of aluminium oxide do any processing in zeolite to measure before adjusting its diffusivity.
Zeolite ZSM-5 and its conventional preparation are described in United States Patent (USP) 3,702,886.Zeolite ZSM-11 and its conventional preparation
It is described in United States Patent (USP) 3,709,979.Zeolite ZSM-12 and its conventional preparation are described in United States Patent (USP) 3,832,449.Boiling
Stone ZSM-23 and its conventional preparation are described in United States Patent (USP) 4,076,842.Zeolite ZSM-35 and its conventional preparation are described in beauty
In state's patent 4,016,245.ZSM-48 and its conventional preparation are instructed by United States Patent (USP) 4,375,573.These United States Patent (USP)s it is complete
Portion's disclosure is hereby incorporated by reference.
Above-mentioned mesopore zeolite is preferably as the size and shape in their hole are relative to other for the method for the present invention
For xylene isomer, production paraxylene is advantageous.However, the conventionally form diffusing parameter values of these zeolites are super
0.1-15sec needed for the method for the present invention out-1Range.However, required diffusion may be implemented by stringent steam treatment zeolite
Property, thus realize that the controlled of catalyst micro pore volume is reduced to 50% not less than non-steam treatment catalyst, preferably 50-
90%.It is supervised by measuring the n-hexane adsorption capacity of zeolite under 90 DEG C and 75 support n-hexane pressure before and after steam
The reduction of micrometer pore volume.
By at least about 950 DEG C, preferably from about 950 DEG C to about 1075 DEG C, and most preferably about 1000 to about 1050 DEG C
At a temperature of heating material about 10 minutes to about 10 hours in the presence of steam, implemented at steam to 5 hours within preferably 30 minutes
Manage the required reduction to realize the micro pore volume of porous crystalline material.
In order to realize the controlled reduction of required diffusivity and micro pore volume, it may be necessary to will be porous before steam treatment
Crystalline material is combined at least one oxide modifier, and the oxide modifier is preferably selected from periodic table (IUPAC editions)
The oxide of IIA, IIIA, IIIB, IVA, VA, VB and Group VIA element.Easily, at least one oxide modifier choosing
From boron, magnesium, calcium, the oxide of lanthanum and preferred phosphorus.In some cases, it can be possible to wish porous crystalline material and more than one oxygen
Compound modifier combination, such as the combination of phosphorus and calcium and/or magnesium realize target diffusion parameter because can reduce in this way
Steam treatment intensity needed for value.It is measured with elemental basis, the total amount of oxide modifier present in catalyst can be with
It is about 0.05 to about 20wt%, for example, about 0.1 to about 10wt%, the weight based on final catalyst.
When modifying agent includes phosphorus, by United States Patent (USP) US4,356,338, US5,110,776, US5,231,064 and
US5, method described in 348,643 are convenient to that modifying agent is added in alkylation catalyst, their complete disclosure
It is hereby incorporated by reference.By closing porous crystalline material (individually or with adhesive or host material combining) with appropriate phosphatization
The solution of object contacts, and then drying and calcination can be realized easily with converting its oxide form for phosphorus with phosphorous chemical combination
The processing of object.Contact with phosphorus-containing compound usually about 25 DEG C and about 125 DEG C at a temperature of carry out it is about 15 minutes to about 20 small
When time.The concentration of phosphorus can be about 0.01 to about 30wt% in contact mixture.
The representative phosphorus-containing compound that can be used for being integrated to phosphorous oxides modifying agent in catalyst includes by PX3, RPX2,
R2PX, R3P, X3PO, (XO)3PO, (XO)3P, R3P=O, R3P=S, RPO2, RPS2, RP (O) (OX)2, RP (S) (SX)2, R2P(O)
OX, R2P (S) SX, RP (OX)2, RP (SX)2, ROP (OX)2, RSP (SX)2, (RS)2PSP(SR)2(RO)2POP(OR)2It indicates
The derivative of group, wherein R is alkyl or aryl, such as phenyl, and X is hydrogen, R or halogen.These compounds include primary, RPH2,
It is secondary, R2PH and uncle, R3P, phosphine such as butyl phosphine, phosphine oxides, R3PO, such as tributylphosphine oxide, tertiary phosphine sulfide, R3PS, primary,
RP(O)(OX)2And secondary, R2P (O) OX, phosphonic acids such as phenyl-phosphonic acid, corresponding sulfur derivatives such as RP (S) (SX)2And R2P (S) SX, phosphine
The ester such as dialkyl alkylphosphonate of acid, (RO)2P (O) H, dialkyl alkylphosphonate, (RO)2P (O) R and alkyl dialkyl phosphinic acid
Ester, (RO) P (O) R2, phosphonous acid, R2POX, such as diethyl phosphonous acid, primary, (RO) P (OX)2, secondary, (RO)2POX and uncle, (RO)3P,
Phosphite ester and its ester, such as single propyl ester, alkyl dialkylphosphinic acids ester, (RO) PR2With dialkyl group alkyl sub-phosphonate, (RO)2PR, esters.Also corresponding sulfur derivatives, including (RS) can be used2P (S) H, (RS)2P (S) R, (RS) P (S) R2, R2PSX,
(RS)P(SX)2, (RS)2PSX, (RS)3P, (RS) PR2, and (RS)2PR.The example of phosphite ester includes Trimethyl phosphite, sub-
Triethyl phosphate, diisopropyl phosphite, phosphorous acid butyl ester and pyrophosphate such as tetraethyl pyrophosphite.In the compound
Alkyl preferably comprise 1-4 carbon atom.
Other suitable phosphorus-containing compounds include ammonium hydrogen phosphate, phosphorus Halides such as phosphorus trichloride, phosphonium bromide and iodate phosphorus, alkyl
Phosphorus dichloride, (RO) PCl2, dialkyl group phosphorus chloride, (RO)2PCl, dialkyl group phosphinidyne chloride, R2PCl, alkyl-alkyl phosphine
Acyl chlorides compound, (RO) (R) P (O) Cl, dialkyl group phosphino- chloride, R2P (O) Cl and RP (O) Cl2.Applicable corresponding sulfur derivatives
Including (RS) PCl2, (RS)2PCl, (RS) (R) P (S) Cl and R2P(S)Cl。
Specific phosphorus-containing compound includes ammonium phosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, chloride 2-phenyl-phosphine, phosphorous acid
Trimethyl, phosphorus trichloride, phosphoric acid, oxychloride phenyl phosphorus, trimethyl phosphate, diphenyl phosphonous acid, diphenyl phosphonic acid, diethyl
Base chlorine thiophosphate, methyl phosphate ester acid and other alcohol-P2O5Reactor product.
Can be used for mixing the representative boron-containing compound in catalyst for boron oxide modified dose includes boric acid, boric acid front three
Ester, boron oxide vulcanize boron, boron hydride, butyl dimethoxy boron, butyl boron dihydroxide, dimethyl boric anhydride, hexamethyl borazole, phenyl
Boric acid, boron triethyl, diborane and triphenyl borine.
Representative magnesium-containing compound includes magnesium acetate, magnesium nitrate, magnesium benzoate, propionic acid magnesium, 2 ethyl hexanoic acid magnesium, carbonic acid
Magnesium, magnesium formate, magnesium oxalate, magnesium bromide, magnesium hydride, magnesium lactate, Magnesium dilaurate, magnesium oleate, magnesium palmitate, magnesium salicylate are stearic
Sour magnesium and magnesium sulfide.
Representative calcium containing compound includes calcium acetate, calcium acetylacetonate, calcium carbonate, calcium chloride, calcium methoxide, aphthenic acids
Calcium, calcium nitrate, calcium phosphate, calcium stearate and calcium sulfate.
The representative lanthanum compound that contains includes lanthanum acetate, lanthanum acetylacetone, lanthanum carbonate, lanthanum chloride, lanthanum hydroxide, nitric acid
Lanthanum, lanthanum orthophosphate and lanthanum sulfate.
The porous crystalline material used in the method for disclosed embodiment can be with various adhesives or host material
Combination, described adhesive or host material are resistant to temperature used in this method and other conditions.These materials include activity and
Non-active material, such as clay, silica and/or metal oxide, such as aluminium oxide.The latter can be it is naturally occurring, or
It is gelatinous precipitate or gel form comprising the mixture of silica and metal oxide.Use active material
Often change the conversion ratio and/or selectivity of catalyst, therefore is not usually preferred.Non-active material is suitable as diluting
Agent obtains product to control the conversion ratio in given method, so as to economy without controlling using other methods in an orderly manner
Reaction rate.These materials can mix in naturally occurring clay, such as bentonite and kaolin, in commercial operating conditions
The lower crushing strength for improving catalyst.The material, i.e. clay, oxide etc., the adhesive as catalyst.It is desirable to provide tool
There is the catalyst of good crushing strength, because in industrial use, it is desirable to prevent catalyst from resolving into dusty material.These are viscous
Soil and/or oxide adhesive are generally used only for improving the crushing strength of catalyst.
Natural clay that can be compound with porous crystalline material includes montmorillonite and kaolin series, including sub- swelling
The kaolin or other main mineral constituents of soil, and commonly referred to as Dixie, McNamee, Georgia and Florida clay is
The kaolin of galapectite, kaolinite, dickite, nacrite or bauxite.These clays can by it is original exploitation or initially into
The state of row calcining, acid processing or chemical modification uses.
In addition to the materials noted above, porous crystalline material can be compound with porous matrix material, such as silica-zirconia
Aluminium, silica-magnesia, silica-zirconium oxide, silica-thorium oxide, silica-beryllia, silica-
Titanium dioxide and ternary composition.Such as silica-alumina-thoria, silica-alumina-zirconium oxide, two
Silicaalumina-magnesia and silica-magnesiazirconia.
The relative scale of porous crystalline material and inorganic oxide matrix changes very greatly, the former content is about 1 to about 90
Weight %, it is more common to be, especially when compound is prepared with bead form, account for about the 2 to about 80wt% of compound.
The condition used in the alkylation stage of the method for the present invention is unrestricted, but in the case where toluene methylation,
Generally include following range: (a) temperature is between about 500 to about 700 DEG C, such as between about 500 DEG C to about 600 DEG C；(b) it presses
Power is that about 1 atmosphere is depressed into about 1000psig (about 100 to about 7000kPa), and (about 170 to about by for example, about 10psig to about 200psig
1480kPa)；(c) mole toluene/mole, of methanol (in reactor charging) is at least about 0.2, for example, about 0.2 to about 20；(d)
The weight (hourly) space velocity (WHSV) (" WHSV ") of total hydrocarbon charging for reactor is about 0.2 to about 1000, such as is for aromatic reactants
About 0.5 to about 500, it is about 0.01 to about 100 for combining each section of methanol reactant stream, based on the whole catalysis in reactor
Agent.
Alkylation can carry out in any of reaction vessel, and wherein every kind of methanol and aromatic feed is with list
In grade or multistage injection reactor beds or bed.In one embodiment, aromatic reactants are being injected into fluidized bed or fixed bed
Position downstream one or more positions by methanol feed segmentation injection reactor beds or multiple reaction beds in.For example,
In one specific embodiment, fluidized-bed reactor can be used, and aromatic feed can be injected to single vertical catalyst
The lower part of fluidized bed, methanol is injected in bed with position among the bed at multiple vertical direction intervals and product takes at the top of bed
Out.Alternatively, catalyst can be set in the catalyst bed at multiple vertical direction intervals, aromatic feed injects the first fluidized bed
Lower part, part methanol injects first middle section and part methanol injects in adjacent downstream catalyst bed or between.
Such as United States Patent (USP) US 6, taught in 642,426, segmentation introduce methanol improve the conversion of methanol and aromatic hydrocarbons with
Generate more advanced methylaromatic compound.Methanol charging can be uniformly distributed in each decanting point, or can be unevenly
Distribution, this depends on the dynamics of reaction and required residence time.For example, if necessary to the longer methanol residence time, it can
The methanol of greater percentage to be injected to the lower decanting point of reactor beds.It, can be with alternatively, if necessary to the less residence time
In the methanol of the higher decanting point injection higher percent of reactor.Those skilled in the art can determine the methanol note of optimization
Enter, according to reactor condition, such as pressure, temperature, the concentration of WHSV and reactants and products improve product yield and distribution
And certain conversion ratios and selective target are influenced, such as and catalyst activity, selectivity and quantity.
In general, by water and methanol charging altogether injection with reduce methanol partial pressure and make methanol to olefin by-products side reaction most
Smallization.The methanol injected in the case where no diluent (such as water) typically results in the light gas by-product of higher amount.It is dilute
Releasing methanol reduces the amount that can be used for side reaction when introducing reactor.In prior art approaches, methanol/water charging contains 25-
The water of 30wt%, the preferably water of 27-29wt%, the total weight based on first alcohol and water.
In one embodiment, the non-purification of methanol containing at least 5wt% water can be used as alkylating agent.Using containing extremely
The non-purification of methanol of few 5wt% water is beneficial because it at least partly reduce (if not completely) by water with
The co-implanted needs of methanol.It will thus be appreciated that at least some embodiments, not additional water with it is unpurified
Methanol cooperatively injects.Unpurified methanol contains the water of about 5-35wt%, the preferably water of 20-35wt%.When not purifying
Methanol contain enough water with dilute methanol and reduce methanol partial pressure and make methanol to olefin by-products side reaction minimize
When, it is co-implanted not need additional water and the charging of unpurified methanol.Although unpurified methanol can be containing trace containing oxidation
Close object, such as ethyl alcohol, propyl alcohol, butanol, amylalcohol, dimethyl ether (DME), methyl formate, methyl acetate, acetone and butanone, such as ability
Known to field technique personnel, such oxygenatedchemicals will not have an adverse effect to alkylated reaction.Such as United States Patent (USP) US 9,
As taught in 006,506, therefore do not need to remove from the charging of unpurified methanol before injecting reactor.
When aromatic device is used in combination with methyl alcohol product installation, had the advantages that using unpurified methanol additional.Cause
Even preferred a large amount of water can be allowed for the methylation of toluene and/or benzene and methanol, so methanol can bypass traditional first
Alcohol purification process (is usually carried out with multiple distillations or fractionating column).Skipping the purification step allows to reduce at least one destilling tower,
This means that saving the capital or ten thousand dollars of 1000-2000 of capital investment of 3-10%.The reduction of tower also saves energy, according to
Estimation, for producing 5 tons of methanol, saving energy is about 18.5MW.
Crude carbinol can also be used for other methanol conversion technologies, such as methanol-to-olefins (it is disclosed in Publication No. 3,894,
107；3,928,483；4,025,571；4,423,274；With 4,433,189 United States Patent (USP)), preparing gasoline by methanol (is disclosed in public affairs
The number of opening is 3,894,103；3,894,104；3,894,107；4,035,430；With 4,058,576 United States Patent (USP)), methanol preparation virtue
Hydrocarbon or any other methanol hydrocarbon conversion process.Reactor for this transformation technology may include fixed bed, moving bed or stream
Change bed, or the other kinds of reactor suitable for methanol conversion.
Other methanol conversion technologies and catalyst also can be used crude carbinol, such as, but not limited to Patent No. 8, and 623,
321；8,609,920；8,609,919 United States Patent (USP)；Publication No. 2005/0070749；2006/0252633；2011/
0082025；2011/0137099；2011/0178356；2011/0174692；2011/0178354；2012/0238789；
2012/0277509；2013/0190546；2013/0296622；2013/0303820；2014/0194663；2014/
0058157；2015/0073187 U.S. Patent Application Publication specification；Publication No. 2003/059509；2015/025327；
2015/184600 PCT Patent Application prospectus；Publication No. 102,964,201；101,829,594；101,885,
662；102,040,460；102,040,459；102,101,818；102,205,251；102,259,019；102,259,018；
102,295,515；102,335,622；102,372,589；102,372,588；102,372,587；102,372,586；102,
372,585；102,372,584；102,372,583；102,372,582；102,464,561；102,464,560；102,464,
559；102,464,558；102,464,557；102,464,550；102,464,549；102,464,540；102,463,136；
102,463,085；102,463,084；102,463,072；102,513,144；102,600,887；102,671,694；102,
688,771；102,716,763；102,731,243；102,701,899；102,746,099；102,746,080；102,744,
111；102,746,098；102,746,095；102,826,957；102,872,904；102,875,321；102,875,320；
102,875,319；102,875,317；102,816,044；102,909,064；102,942,441；102,951,993；102,
964,201；103,113,182；103,121,912；103,121,911；103,120,949；103,263,946；103,372,
456；103,418,421；103,467,238；103,588,611；103,588,610；103,588,601；103,638,963；
103,664,492；103,664,490；103,664,488；103,664,484；103,708,496；103,772,129；103,
769,246；103,785,464；103,785,463；103,785,461；103,801,402；103,803,581；103,804,
112；103,816,935；103,878,014；103,980,080；104,096,589；104,109,065；104,117,385；
104,117,384；104,128,198；104,226,357；104,051,639；104,226,359；104,230,633；104,
292,064；104,275,209；104,326,855；104,342,198；104,415,784；104,437,599；104,492,
476；104,447,158；104,557,425；104,557,376；104,549,452；104,710,268；104,710,265；
104,874,418；104,888,846；104,945,219；104,909,980；105,080,593；105,198,691；105,
214,714；104,981,695；105,272,798；105,272,797；105,315,120；105,344,373；105,439,
790；105,457,670；105,115,333 Chinese patent application prospectus；Specially with 2013/066884 Japan of Publication No.
Sharp ublic specification of application.
Although describe and illustrating the present invention by reference to particular implementation, those of ordinary skill in the art will be managed
Solution, without departing from the spirit and scope of the present invention, the present invention are suitable for change and modification, these change and modification are not
One is scheduled on this disclosure.Accordingly, it is not intended that scope of the appended claims are limited to example described in this specification
And description, but claims is construed as all features comprising existing patentability novelty herein, including will be by this
Apply one of ordinary skill in the art as all features of its equivalent.
The product name that this specification uses byTMSymbol orSymbol indicates, shows that these titles may be by particular brand
The protection of right, for example, they may be the registered trademark of each jurisdiction.All patents and patent applications test journey
Sequence (such as ASTM method, UL method etc.) and the alternative document of this specification reference are incorporated as referring to by whole, model
Enclose so that it is disclosed above with this specification not contradiction and for it is disclosed above be all to allow for all compasses of competency
's.When listing numerical lower limits and numerical upper limits herein, cover the range from any lower limit to any upper limit.Term "comprising" with
Term " includes " is synonymous.Equally, no matter when composition, element or group subassembly before have transition conjunctive phrase "comprising",
It should be understood that we also consider that the composition, component or multiple component congregation zones have transition phrase " substantially by ... group
At ", " consist of ", " being selected from " or "Yes" are before the constituent, component or multiple components, and vice versa.
Claims (19)
1. a kind of make toluene and/or benzene be alkylated the method to produce paraxylene, it is included in alkylation reactor
Make the toluene and/or benzene and alkylating agent under alkylation conditions in the presence of alkylation catalyst, includes pair to generate
The alkylation effluent of dimethylbenzene, improving includes using unpurified methanol as alkylating agent, wherein unpurified methanol
Containing at least water of 5wt%, the weight based on unpurified methanol.
2. the method for claim 1 wherein unpurified methanol to contain the water of 20-35wt%, the weight based on unpurified methanol
Amount.
3. method for claim 2, co-implanted without additional water and unpurified methanol.
4. the method for claim 1 wherein unpurified methanol to contain the water less than 28wt%, the weight based on unpurified methanol
Amount, and additional water and unpurified methanol is co-implanted the amount of water is increased to about 28wt%, based on unpurified
The total weight of first alcohol and water.
5. the method for any one of claim 2 or 4, wherein unreacted methanol is injected along reactor axis to multistage.
6. the method for any one of claim 2 or 4, wherein alkylation catalyst is porous crystalline material, when in 120 DEG C of temperature
Degree and 2 when measuring under 60 support of 2- dimethylbutane pressure (8 kPas), has about 0.1-15sec-12,2- dimethyl butyrate
The diffusion parameter of alkane.
7. method for claim 6, wherein alkylation catalyst is selected from ZSM-5, ZSM-11, ZSM-12, ZSM-22, ZSM-
23, the intermediate pore size aluminosilicate zeolite of ZSM-35 and ZSM-48, it is optionally compound with inorganic oxide matrix.
8. the method for any one of claim 2 or 4, wherein alkylation conditions include about 500 to about 700 DEG C of temperature, about 1 is big
Pressure of the air pressure to (about 100 to about 7000kPa) about 1000psig, the molar ratio of toluene and methanol (in reactor charging)
It is at least about 0.2, and being fed into the weight (hourly) space velocity (WHSV) (" WHSV ") of whole hydrocarbon of reactor is about 0.2 to about 1000, based on anti-
Answer the total catalyst in device.
9. the method for any one of claim 2 or 4, wherein alkylation effluent includes at least paraxylene of 85wt%.
10. a kind of method for preparing paraxylene, this method comprises:
(a) make under alkylating conditions in the presence of alkylation catalyst in alkylation reactor toluene and/or benzene with it is impure
The methanol of change contacts, to generate the alkylation effluent for including paraxylene, wherein unpurified methanol contains at least 5wt%'s
Water, the weight based on unpurified methanol；And
(b) paraxylene is recycled from alkylation effluent.
11. method for claim 10, wherein unpurified methanol contains the water of 20-35wt%, based on unpurified methanol
Weight.
12. the method for claim 11, co-implanted without additional water and unpurified methanol.
13. method for claim 10, wherein unpurified methanol contains the water less than 28wt%, based on unpurified methanol
Weight, and additional water and unpurified methanol is co-implanted the amount of water is increased to about 28wt%, based on not purifying
First alcohol and water total weight.
14. the method for any one of claim 11 or 13, wherein unreacted methanol is injected along reactor axis to multistage.
15. the method for any one of claim 11 or 13, wherein alkylation catalyst is porous crystalline material, when at 120 DEG C
Temperature and 2, when measuring under 60 support of 2- dimethylbutane pressure (8 kPas), there is about 0.1-15sec-12,2- diformazan
The diffusion parameter of base butane.
16. the method for claim 15, wherein alkylation catalyst is selected from ZSM-5, ZSM-11, ZSM-12, ZSM-22, ZSM-
23, the intermediate pore size aluminosilicate zeolite of ZSM-35 and ZSM-48, it is optionally compound with inorganic oxide matrix.
17. the method for any one of claim 11 or 13, wherein alkylation conditions include about 500 to about 700 DEG C of temperature, about
1 atmosphere is depressed into the pressure of (about 100 to about 7000kPa) about 1000psig, the molar ratio of toluene and methanol (in reactor charging)
Example is at least about 0.2, and the weight (hourly) space velocity (WHSV) (" WHSV ") of total hydrocarbon charging for reactor is about 0.2 to about 1000, is based on
Whole catalyst in reactor.
18. the method for any one of claim 11 or 13, wherein alkylation effluent includes at least paraxylene of 85wt%.
19. the method for any one of claim 11 or 13, wherein being returned from alkylation effluent by moving-bed adsorption
Receive paraxylene.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US201662430021P | 2016-12-05 | 2016-12-05 | |
| US62/430,021 | 2016-12-05 | ||
| EP17150624 | 2017-01-09 | ||
| EP17150624.9 | 2017-01-09 | ||
| PCT/US2017/058991 WO2018106357A1 (en) | 2016-12-05 | 2017-10-30 | Process of producing paraxylene by the methylation of toluene and/or benzene |
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| CN109963827A true CN109963827A (en) | 2019-07-02 |
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| CN201780070746.1A Pending CN109963827A (en) | 2016-12-05 | 2017-10-30 | The method for preparing paraxylene by the methylation of toluene and/or benzene |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1352627A (en) * | 1999-09-23 | 2002-06-05 | 埃克森美孚石油公司 | Process for converting methanol or dimethyl ether to olefins |
| CN102372582A (en) * | 2010-08-23 | 2012-03-14 | 中国石油化工股份有限公司 | Fluidized catalytic method for toluene methylation |
| US20130296622A1 (en) * | 2012-05-07 | 2013-11-07 | Larry L. Iaccino | Process for the Production of Xylenes and Light Olefins |
| CN104936931A (en) * | 2013-01-31 | 2015-09-23 | 埃克森美孚化学专利公司 | Production of para-xylene |
| WO2016081110A1 (en) * | 2014-11-21 | 2016-05-26 | Exxonmobil Chemical Patents Inc. | Process for making para-xylene |
-
2017
- 2017-10-30 CN CN201780070746.1A patent/CN109963827A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1352627A (en) * | 1999-09-23 | 2002-06-05 | 埃克森美孚石油公司 | Process for converting methanol or dimethyl ether to olefins |
| CN102372582A (en) * | 2010-08-23 | 2012-03-14 | 中国石油化工股份有限公司 | Fluidized catalytic method for toluene methylation |
| US20130296622A1 (en) * | 2012-05-07 | 2013-11-07 | Larry L. Iaccino | Process for the Production of Xylenes and Light Olefins |
| CN104936931A (en) * | 2013-01-31 | 2015-09-23 | 埃克森美孚化学专利公司 | Production of para-xylene |
| WO2016081110A1 (en) * | 2014-11-21 | 2016-05-26 | Exxonmobil Chemical Patents Inc. | Process for making para-xylene |
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