CN110023458A

CN110023458A - For producing combination alkene and the oxygenate conversion of aromatic hydrocarbons

Info

Publication number: CN110023458A
Application number: CN201780074982.0A
Authority: CN
Inventors: B·J·奥尼尔; S·J·麦卡锡
Original assignee: ExxonMobil Research and Engineering Co
Current assignee: ExxonMobil Technology and Engineering Co
Priority date: 2016-12-07
Filing date: 2017-11-09
Publication date: 2019-07-16
Also published as: JP2020513459A; KR20190093620A; WO2018106397A1; US20180155631A1

Abstract

Provide the system and method for oxygenate method for transformation in reaction environment including alkene.For being related to the method for transformation of the zeolite catalyst of metal promoted, when catalyst is exposed to charging, alkene, which is added, into oxygenate-containing feedstock can reduce or minimize the loss of arenes selectivity.Additionally or as selection, for being related to the method for transformation of the zeolite catalyst comprising the zeolite in addition to MFI Framework-type zeolite, when catalyst is exposed to charging, alkene, which is added, into oxygenate-containing feedstock can reduce or minimize the loss of oxygenate activity of conversion.

Description

For producing combination alkene and the oxygenate conversion of aromatic hydrocarbons

Field

The present invention relates to form naphtha boiling-range product (including virtue by conversion oxygenate (oxygenate) and alkene Hydrocarbon) integrated approach.

Background

Known a variety of commercial runs are used to convert higher value product for low boiling point carbon compound.For example, methanol system Gasoline (MTG) is the business method for preparing gasoline by methanol using ZSM-5 catalyst.In MTG technique, first by methanol dehydration For dimethyl ether.Then methanol and/or dimethyl ether react in series reaction, result in aromatic hydrocarbons, alkane and olefinic compound Object.Products therefrom is made of liquefied petroleum gas (LPG) and the premium-type gasoline comprising aromatic hydrocarbons, alkane and alkene.Typical MTG Hydrocarbon products add alkene and the alkane of about 50-60% to form by the aromatic hydrocarbons of about 40-50%.

United States Patent (USP) 3,894,104, which is described, converts virtue for oxygenate using the zeolite catalyst for being impregnated with transition metal The method of hydrocarbon.It is reported that aromatic hydrocarbons relative to total hydrocarbon products high income of about 58%, corresponding total C₅+ high income is of about 73%.

U.S. Patent Application Publication 2013/0281753 describes the zeolite catalyst of P Modification.It is exposed to and contains in catalyst After having the environment of steam, P Modification reduces the variation of the α value of catalyst.P Modification catalyst is described as being suitable for for example Methanol is converted into gasoline-range compound.

U.S. Patent Application Publication 2015/0174561,2015/0174562 and 2015/0174563 is described for by oxygen Close the catalyst that object is converted into aromatic hydrocarbons.Catalyst includes zeolite, such as MFI or MEL skeleton structure zeolite, is had on a catalyst 12nd race's metal of load.

United States Patent (USP) 9,090,525, which describes, converts oxygenate in the presence of a zeolite catalyst to be formed with increased pungent The naphtha boiling-range compound of alkane value.By a part of naphtha boiling-range olefin recycle from initial conversion product to oxygenate To form heavier naphtha boiling-range compound, including aromatic hydrocarbons in method for transformation.

Abstract

In some respects, a kind of method for forming naphtha composition is provided.This method may include will include oxygenate The charging of (such as methanol) and alkene is exposed to reforming catalyst.The example of effective conversion condition may include about 300 DEG C to about 550 DEG C average reaction temperature, the gross pressure and/or 0.1h of about 10psig (~70kPag) to about 400psig (~2700kPag)^-1 To 20.0h^-1WHSV.Charging, which is exposed to reforming catalyst, can lead to the conversion outflow to be formed comprising naphtha boiling-range fraction Object.Naphtha boiling-range fraction can have at least 80 octane number and/or may include relative to conversion effluent in hydrocarbon total weight Less than CO, CO of 6.0 weight %₂And CH₄Combination.Charging can have about 1 to about 20 oxygenate and olefin molar ratio.Turn Change catalyst, which may include at least zeolite with MFI skeleton structure of 10 weight %, the zeolite, optionally has 10 to 200 Silica alumina ratio and at least 5 α value.The conversion that is supported on that reforming catalyst can further include 0.1 weight % to 3.0 weight % is urged Transition metal in agent, such as the zinc being supported on reforming catalyst.

Optionally, naphtha boiling-range fraction can have at least 90 (or at least 93, or octane number at least 97) and/or opposite In the weight at least about aromatic hydrocarbons of 40 weight % of naphtha boiling-range fraction.Optionally, average reaction temperature can be at least about 400 DEG C, or at least about 450 DEG C.

In some respects, the method to form naphtha composition is provided.This method may include will comprising oxygenate (such as Methanol) and the charging of alkene be exposed to reforming catalyst.The example of effective conversion condition may include about 300 DEG C to about 550 DEG C Average reaction temperature, about 10psig (~70kPag) to about 400psig (~2700kPag) gross pressure and/or 0.1hr^-1Extremely 20.0hr^-1WHSV.Charging, which is exposed to reforming catalyst, can lead to form conversion effluent, and conversion effluent includes naphtha Boiling fraction and optionally also comprising relative to conversion effluent in hydrocarbon total weight be at least about the alkene of 30 weight % and/ Or the oxygenate less than 15 weight %.Charging can have 1 to 20 oxygenate and olefin molar ratio.Reforming catalyst can wrap Containing at least 10 member rings of 10 weight % or 12 member ring zeolites, there is the skeleton structure different from MFI skeleton structure.Zeolite can appoint Selection of land has 10 to 200 silica alumina ratio and/or at least 5 α value.Reforming catalyst optionally also includes 25 grams to 200 grams oxygen Close the average catalyst exposure duration of every gram of catalyst of object.Reforming catalyst optionally further includes 0.1 weight % to 3.0 The transition metal of weight % being supported on reforming catalyst, such as Zn.

Optionally, reforming catalyst may include the average catalyst exposure duration of every gram of catalyst of 50 grams to 200 grams methanol (or 25 grams to 180 grams or 50 grams to 180 grams or 50 grams to 150 grams or 100 grams to 200 grams).Optionally, reforming catalyst It may include the zeolite of the skeleton structure with MRE (ZSM-48), MTW, TON, MTT, MFS or combinations thereof of at least 10 weight %.

In terms of optional, it includes the charging that will include oxygenate that the charging comprising oxygenate, which is exposed to reforming catalyst, Be exposed to reforming catalyst in fluidized bed, moving bed, riser reactor or combinations thereof, reforming catalyst be removed and with The rate for being equivalent to 0.3 weight % of oxygenate to 3.0 weight % catalyst regenerations that every 1 anti-violence is exposed to gram reforming catalyst regenerates (optional 1.5 weight % to 3.0 weight %).

In some respects, reforming catalyst can further include the phosphorus being supported on reforming catalyst, on reforming catalyst The molar ratio of phosphorus and zinc is optionally 1.5 to 3.0.Additionally or as selection, the charging comprising oxygenate and alkene includes containing extremely First raw material of few a part of oxygenate and the second raw material containing at least part alkene, the first raw material and the second raw material into It is mixed after entering the reactor containing reforming catalyst.

In terms of some optional, a) charging can include about the oxygenate of 30 weight % to about 95 weight %, about 5 weight % To the alkene of about 40 weight %, or combinations thereof；B) charging may include at least about 20 weight % to about 60 weight % different from oxygen Close the component of object and alkene, or about 40 weight % to 60 weight %；Or c) combination a) and b).

On the other hand, oxygenate conversion effluent is provided.Relative to the total weight of hydrocarbon in conversion effluent, oxygenate Conversion effluent may include the aromatic hydrocarbons of at least 40 weight %, less than CO, CO of 6.0 weight %₂And CH₄Combination, and less than 10 The alkene of weight %.The naphtha boiling-range part of conversion effluent can have at least 90 octane number.Optionally, relative to aromatic hydrocarbons Total weight is that the aromatic hydrocarbons less than 10 weight % includes C₁₀Aromatic hydrocarbons, and/or relative to C₁₀Aromatic hydrocarbons total weight is less than 10 weight %'s C₁₀Aromatic hydrocarbons includes durene.Optionally, oxygenate conversion effluent may include less than CO, CO of 5.0 weight %₂And CH₄Combination. Optionally, relative to C₁₀The total weight of aromatic hydrocarbons, less than the C of 5 weight %₁₀Aromatic hydrocarbons includes durene, or combinations thereof.

The brief description of accompanying drawing

Fig. 1 schematically shows the example for converting the reaction system that oxygenate is alkene.

Fig. 2 shows the result that methanol is converted in the presence of various zeolite catalysts.

Fig. 3 shows the opposite receipts that methanol and methanol add 1- amylene to convert in the presence of 1 weight %Zn-ZSM-5 catalyst Rate.

Fig. 4 shows the result that methanol converts at various temperatures in the presence of ZSM-5 catalyst.

Fig. 5 shows the result that methanol and 1- amylene convert at various temperatures in the presence of ZSM-5 catalyst.

Fig. 6 shows the yield advantage that methanol and methanol add 1- amylene to convert in the presence of ZSM-5 catalyst.

Fig. 7 shows another yield advantage point that methanol and methanol add 1- amylene to convert in the presence of ZSM-5 catalyst Analysis.

Fig. 8 shows the opposite aromatics yield that methanol and methanol add 1- amylene to convert in the presence of ZSM-5 catalyst.

Fig. 9 shows that methanol and methanol add 1- amylene to convert relatively fragrant in the presence of 1 weight %Zn-ZSM-5 catalyst Hydrocarbon yield.

Figure 10 shows the result that methanol converts in the presence of ZSM-48 catalyst.

Figure 11 shows the result that methanol adds 1- amylene to convert in the presence of ZSM-48 catalyst.

Detailed description of the invention

In all fields, it provides for converting oxygenate (such as methanol or dimethyl ether) and the combined feed of alkene to The system and method for high-octane naphtha boiling range product.For being related to the method for transformation of metal promoted zeolite catalyst, when urging When agent is exposed to charging, alkene, which is added, into oxygenate-containing feedstock can reduce or minimize the loss of arenes selectivity.In addition Or alternatively, for being related to the method for transformation of the zeolite catalyst in addition to MFI framework types, when catalyst is exposed to charging When, alkene, which is added, into oxygenate-containing feedstock can reduce or minimize the loss of oxygenate activity of conversion.

Natural gas, coal and/or biomass are just becoming the more and more important carbon for producing fuel and/or lubricant product Source.The first step of the conversion of carbon from natural gas, coal and/or biomass sources can be methane and be converted into methanol.Once being formed Methanol can be used various fixed beds, fluidized bed and moving bed process and convert methanol into higher value product, such as fuel, Aromatic hydrocarbons and/or alkene.Zeolite catalyst such as MFI skeleton (ZSM-5) zeolite catalyst can be used in this method.

Converting methanol into naphtha boiling-range product (such as aromatic hydrocarbons) may be with zeolite catalysis as some difficulties of gasoline The trend that agent relatively quickly inactivates is related.Aromatic selective can also be will lead to even if relatively small charging exposure zeolite catalyst Property loss, correspondingly increase lesser value alkane formation.For the zeolite skeleton in addition to MFI, catalyst inactivation is also It can influence the general ability of oxygenate in catalyst conversion charging.

A kind of selection for improving the arenes selectivity of zeolite catalyst can be the transition gold that load is added on a catalyst Belong to the formation to promote aromatic hydrocarbons.Zinc is an example of suitable transition metal, to improve arenes selectivity.Although zinc can be effective Ground improves the initial arenes selectivity of zeolite catalyst, such as MFI skeleton zeolite catalyst, but is exposed to oxygenate-containing feedstock and can lead Catalyst is caused to lose arenes selectivity since oxygenate is converted into oxycarbide and alkane.

Oxygen conjunction is being exposed to unexpectedly, it has been found that alkene is added into oxygenate-containing feedstock and can reduce or minimize The loss of catalyst activity and/or selectivity during object is fed.Alkene can correspond to any C for facilitating type₂-C₆Alkene.? Some aspects, alkene can correspond to the alkene generated during oxygenate method for transformation.In these areas, method for transformation is come from A part of effluent can recycle with provide for charging alkene.In other respects, alkene can derived from it is any its His convenient source.Olefin feedstocks can be optionally included in method for transformation the chemical combination for serving as inert substance or serving as diluent Object.For example, " useless " olefin stream that olefin(e) centent is 5 volume % to 20 volume % can be suitable as alkene source, as long as " useless " alkene The other components of hydrocarbon stream are compatible with method for transformation.For example, the other components of olefin stream can correspond to inert gas such as N₂、 Oxycarbide, alkane and/or other gases at conversion conditions with hypoergia.There may also be water, but preferred water 20 volume % or less or 10 volume % or less corresponding to combined feed.

In the discussion, octane number is defined as (RON+MON)/2, and wherein RON is research octane number (RON), and MON is motor method Octane number.The value recorded in for the examples below, RON and MON value determine that the model, which determines, is based on group based on the model of announcement The octane number of the blend divided, to determine blending octane rating.The model is described in Ind Eng Chem Res 2006,45,337- 345.The model is considered related to the determining value of experiment.In the following claims, research octane number (RON) (RON) basis ASTM D2699 measurement.Motor octane number (MON) is measured according to ASTM D2700.

In the discussion, naphtha boiling-range is defined as 50 °F, and (~10 DEG C, correspond roughly to the most low boiling of pentane isomers Point) to 350 °F (177 DEG C).The boiling range that distillates fuel is defined as 350 °F (177 DEG C) to 700 °F (371 DEG C).Boiling point is lower than naphtha Compound (the C of boiling range_4-) it can be described as light fraction.It should be noted that due to hydrocarbon fraction fractionation (or other based on boiling point point From) during practical consideration, according to methods described herein formed fuel fraction can have corresponding to above-mentioned value T5 and T95 steaming Point (or T10 and T90 distillation point) is evaporated, rather than there is just/final boiling point corresponding to above-mentioned value.It can be used in spite of various methods Determine the boiling point information of given sample, but for following claim, ASTM D86 is the distillation point for determining composition The appropriate method of (distilling point including weight fraction).

Raw material and product-oxygenate conversion

In all fields, catalyst as described herein can be used for converting oxygenate-containing feedstock to aromatic hydrocarbons and/or olefin product, Such as contain at least one C₁-C₄The oxygenate of alkyl and/or other oxygenates.The example of suitable oxygenate includes containing first Alcohol, dimethyl ether, C₁-C₄Alcohol has C₁-C₄The charging of the ether of alkyl chain, it is described that there is C₁-C₄The ether of alkyl chain includes containing C₁-C₄ The asymmetrical ether (such as methyl ethyl ether, butyl ether or methyl-propyl ether) and symmetrical ether (such as diethyl ether, dipropyl of alkyl chain Ether or butyl oxide), or combinations thereof.It should be noted that containing at least one C₁-C₄The oxygenate of alkyl, which is intended to clearly determine to have, to be contained The oxygenate of the alkyl of about 4 carbon or less carbon.Preferably, oxygenate-containing feedstock may include one kind or more of at least about 30 weight % The suitable oxygenate of kind, or at least about 50 weight %, or at least about 75 weight %, or at least about 90 weight %, or at least about 95 Weight %.Additionally or as selection, oxygenate-containing feedstock may include the methanol of at least about 50 weight %, for example, at least about 75 weight % Methanol, or the methanol of at least about 90 weight %, or the methanol of at least about 95 weight %.Particularly, oxygenate-containing feedstock may include The oxygenate (or methanol) or 50 weight % to 95 weight % or 75 weight % to 100 weights of 30 weight % to 100 weight % Measure % or 75 weight % to 95 weight %.Oxygenate-containing feedstock can come from any convenient source.For example, oxygenate-containing feedstock can With by reforming natural gas charging in hydrocarbon to form synthesis gas (H₂, CO, CO₂), then using synthesis gas formed methanol (or its Its alcohol) it is formed.As another example, suitable oxygenate-containing feedstock may include that methanol, dimethyl ether or combinations thereof are closed as oxygen Object.

Beyond the region of objective existence is closed in deoxygenation, and charging also may include alkene.In the discussion, alkene that a part as charging includes can be with Corresponding to the aliphatic olefin containing 6 carbon or less carbon, so that alkene suitably forms naphtha boiling-range compound.It is used for entering Before the reactor for carrying out oxygenate conversion, the hydrocarbon fraction of charging can be mixed with oxygenate, or can be anti-in conversion Answer the multiple streams containing oxygenate and/or alkene of mixing in device.Charging can include about the alkene of 5 weight % to about 40 weight % (that is, alkene containing 6 carbon or less carbon), or about 5 weight % to about 30 weight %, or about 10 weight % to about 40 weights Measure %, or about 10 weight % to about 30 weight %.It is without being bound to any particular theory, it is believed that alkene can effective competition zeolite urge Active sites in agent, zeolite catalyst, which is converted into alkane or oxycarbide to oxygenate, has high activity, such as methanol turns Turn to methane.In order to enable this competition performance that alkene to be made to inhibit undesirable activity, the molar ratio of oxygenate and alkene can To be 20 or lower or 10 or lower or 6.0 or lower or 4.0 or lower, such as down to about 1.0 molar ratio.It should be noted that The weight percent of alkene may depend on the property of alkene in charging.For example, if using C₅Alkene is as feeding containing methanol Alkene, due to C₅The molecular weight of alkene is much bigger, and olefin feed weight % needed for reaching the required molar ratio of alkene and oxygenate will It is relatively high.

Other than oxygenate and alkene, charging can also include diluent, such as water (in vapour form), nitrogen or its His inert gas and/or alkane or other non-reactive hydrocarbons.In some respects, source olefins can correspond to the alkene of low-purity Hydrocarbon source, so that source olefins correspond to 20 weight % or less alkene.In some respects, correspond to and be different from oxygenate and alkene The feeding part of component can correspond to the 1 weight % to 60 weight % or 1 weight % of charging to 25 weight %, or about 10 Weight % to about 30 weight %, or about 20 weight % to about 60 weight %.Optionally, charging can correspond essentially to oxygenate and Alkene, so that the content for being different from the component of oxygenate and alkene is 1 weight % or lower (such as down to 0 weight %).

In some respects, such as with the oxygenate of MFI or MEL skeleton catalyst is used related aspect, aromatic hydrocarbons phase are converted 35 weight % to about 60 weight % can be about for the yield of total hydrocarbon products, or about 38 weight % are to about 60 weight %, or about 40 Weight % to about 52 weight %, or about 38 weight % to about 45 weight %.For example, aromatic hydrocarbons can be relative to the yield of total hydrocarbon products At least about 35 weight %, or at least about 38 weight %, or at least about 40 weight %, or at least about 45 weight %.Additionally or as Selection, aromatic hydrocarbons can be about 60 weight % or lower, or about 55 weight % or lower, or about 52 weights relative to the yield of total hydrocarbon products Measure % or lower, or about 50 weight % or lower.In all fields, alkene can be about 2.0 weights relative to the yield of total hydrocarbon products Measure % to about 30 weight %, or about 2.0 weight % to 25 weight %, or about 5.0 weight % to about 20 weight %, or about 10 weights Measure % to about 20 weight %.For example, alkene can be at least about 2.0 weight % relative to the yield of total hydrocarbon products, or at least about 5.0 Weight %, or at least about 10 weight %.Additionally or as selection, alkene can be about 30 weight % relative to the yield of total hydrocarbon products Or it is lower, or about 25 weight % or lower, or about 20 weight % or lower.In all fields, alkane is relative to total hydrocarbon products Yield can be about 20 weight % to about 45 weight %, or about 20 weight % to about 35 weight %, or about 25 weight % to about 45 Weight %, or about 25 weight % to about 40 weight %.For example, alkane can be at least about 20 relative to the yield of total hydrocarbon products Weight %, or at least about 25 weight %, or at least about 30 weight % and/or alkane can be relative to the yield of total hydrocarbon products About 45 weight % or lower, or about 40 weight % or lower, or about 35 weight % or lower.In the following claims, sample The relative quantity of product paraffin, alkene and aromatic hydrocarbons can be measured according to ASTM D6839.For being generated during oxygenate converts Alkane and alkene, the alkene of at least 50 weight % can correspond to C₃And C₄The alkane of alkene and/or at least 50 weight % It can correspond to C₃And C₄Alkane.Additionally or as selection, the alkane less than 10 weight % can correspond to C₁Alkane (methane).

In some respects, such as with the oxygenate of MRE skeleton catalyst is used related aspect is converted, aromatic hydrocarbons is relative to total The yield of hydrocarbon products can be about 5 weight % to about 30 weight %, or about 10 weight % to about 30 weight %, or about 10 weight % are extremely About 25 weight %, or about 5 weight % to about 20 weight %.For example, aromatic hydrocarbons can be at least about 5 weights relative to the yield of total hydrocarbon products Measure %, or at least about 10 weight %, or at least about 15 weight %.Additionally or as selection, receipts of the aromatic hydrocarbons relative to total hydrocarbon products Rate can be about 30 weight % or lower, or about 25 weight % or lower, or about 20 weight % or lower.In all fields, alkene Yield relative to total hydrocarbon products can be about 20 weight % to about 60 weight %, or about 25 weight % are to 60 weight %, or about 20 Weight % to about 40 weight %, or about 25 weight % to about 50 weight %.For example, alkene can be relative to the yield of total hydrocarbon products At least about 20 weight %, or at least about 25 weight %, or at least about 30 weight %.Additionally or as selection, alkene is relative to total The yield of hydrocarbon products can be about 60 weight % or lower, or about 50 weight % or lower, or about 40 weight % or lower.Each Aspect, alkane can be about 20 weight % to about 50 weight %, or about 20 weight % to about 35 relative to the yield of total hydrocarbon products Weight %, or about 25 weight % to about 45 weight %, or about 25 weight % to about 40 weight %.For example, alkane is relative to total The yield of hydrocarbon products can be at least about 20 weight %, or at least about 25 weight %, or at least about 30 weight % and/or alkane Yield relative to total hydrocarbon products can be about 50 weight % or less, or about 45 weight % or less, or about 40 weight % or Less, or about 35 weight % or less.For the alkane and alkene generated during oxygenate converts, at least 50 weight %'s Alkene can correspond to C₃And C₄The alkane of alkene and/or at least 50 weight % can correspond to C₃And C₄Alkane.In addition or Alternatively, the alkane less than 10 weight % can correspond to C₁Alkane (methane).

The total hydrocarbon products converted in effluent may include naphtha boiling-range part, the boiling range that distillates fuel part and light fraction portion Point.Optionally but preferably, conversion effluent may include compound of the boiling point less than 1.0 weight % higher than the boiling range that distillates fuel (371 DEG C+) such as have 371 DEG C or lower final boiling point.In all fields, selectivity/stone of naphtha boiling-range part is formed The yield of cerebrol boiling range part can be at least about 35 weight % and/or about 75 weight % or lower.For example, forming naphtha boiling The selectivity of journey part/naphtha boiling-range part yield can be about 35 weight % to 75 weight % or 40 weight % to 65 weights Measure % or 40 weight % to 60 weight % or 45 weight % to 70 weight %.

The naphtha boiling-range part formed by method for transformation can have at least 80, or at least 90, or at least 95, or at least 97, or at least 100, or at least 102, or at least 105, such as up to 110 octane number.Particularly, it is being related to MFI or MEL skeleton The aspect of catalyst, octane number can be 80 to 110 or 95 to 110 or 97 to 110 or 100 to 110.Additionally or as choosing It selects, in terms of being related to MRE skeleton catalyst, octane number can be 80 to 97 or 90 to 97.As defined above, octane number is corresponding In (RON+MON)/2).

Conversion condition can also result in CO and/or CO₂Generation.In some respects, CO, CO₂And CH₄Combined amount can be with Corresponding to the about 6.0 weight % or less of total hydrocarbon products in conversion effluent, or about 5.0 weight % or less.In this discussion and In following claim, when amount (such as weight of total hydrocarbon products) of the total hydrocarbon products of determination, including CO in conversion effluent And CO₂Amount.

The suitable and/or condition for validity for carrying out conversion reaction may include about 3000 DEG C to about 550 DEG C, and (or about 350 DEG C to about 550 DEG C, or about 400 DEG C to about 500 DEG C) average reaction temperature, about 10psig (70kPag) to about 400psig (~ 2700kPaa) or about 50psig (~350kPag) to about 350psig (~2400kPag) or about 100psig (~700kPag) Gross pressure between about 300psig (~2100kPag), about 0.1hr^-1To about 10hr^-1Between oxygenate air speed, be based on oxygen Close weight of the weight of object relative to catalyst.For example, average reaction temperature can be at least about 300 DEG C, or at least about 350 DEG C, or at least about 400 DEG C, or at least about 450 DEG C.Additionally or as selection, average reaction temperature can be about 550 DEG C or lower, Or about 500 DEG C or lower, or about 450 DEG C or lower, or about 400 DEG C or lower.In the discussion, average reaction temperature is defined as Wherein carry out the reactor inlet temperature of the reactor of conversion reaction and the average value of reactor outlet temperature.As another reality Example, gross pressure can be at least about 70kPag, or at least about 350kPag, or at least about 500kPag, or at least about 700kPag, Or at least about 1000kPag.Additionally or as selection, gross pressure can be about 3000kPag or lower, or about 2700kPag or more It is low, or about 2400kPag or lower, or about 2100kPag or lower

It is optionally possible to include using a part fed as conversion reactor by a part conversion effluent recycling. For example, at least part light fraction for carrying out inverting effluent can be recycled as a part of charging.Light fraction follows again Loop section can correspond to any convenient amount, such as 25 weight % are to the light fraction of 75 weight %.The recycling of light fraction can To provide alkene, the other reactant in conversion reaction may be used as, and provide temperature controlled mechanism.

Various types of reactors can provide the suitable configurations for carrying out conversion reaction.Suitable reactor may include Fixed bed reactors (such as trickle bed reactor), moving-burden bed reactor (such as riser reactor) and fluidized-bed reactor.It should infuse Meaning, the activity and/or selectivity of the catalyst for oxygenate conversion can be exposed to the oxygenate-containing feedstock of incrementss with catalyst And change.The variation for thinking this catalyst activity is due to forming coke on a catalyst.When in fixed bed reactors into When row oxygenate converts, calculating average catalyst exposure duration be can be directly, because introducing the amount of the oxygenate of reactor It can be compared with the amount of the reforming catalyst in reactor.This can be used for calculating average catalyst exposure duration, as The grams of the oxygenate (such as methanol) of catalyst is exposed to divided by the ratio of the grams of catalyst.

With the increase of average catalyst exposure duration, the variation of catalyst activity and/or selectivity can be at least partly It is reversed by regenerated catalyst on ground.In some respects, it can be regenerated completely on a catalyst, so that in regenerated catalyst The average magnitude of existing coke is less than 0.1 weight %.In other respects, partial regeneration can be carried out, is urged so that being regenerated after regeneration The average magnitude of coke present on agent is greater than 0.1 weight %.The average magnitude of coke present on catalyst sample can pass through Thermogravimetric analysis is readily determined.

It can be taken out from reactor in catalyst for regenerating and in reactor such as moving-burden bed reactor and/or fluidized bed The aspect recycled during the operation of reactor, catalyst can take out and be replaced with supplement (fresh) and/or regenerated catalyst. It should be noted that being different from completely removing from reaction system catalyst and with fresh for regenerating from catalyst is taken out in reactor It supplements catalyst and replaces the catalyst removed.In the discussion, (remained in regenerated catalyst when being regenerated completely to catalyst Remaining average coke is less than 0.1 weight %), the average catalyst exposure duration of regenerated catalyst is defined as zero, to determine reaction The average catalyst exposure duration of catalyst in device.In these areas, when being regenerated completely, catalyst is exposed to oxygen conjunction The average catalyst exposure duration of object can be based on a) relative to the amount of catalyst reactor, into the oxygenate of reactor The mean residence time of flow rate and b) catalyst in the reactor determines.These values can determine every gram of catalysis in reactor The oxygenate average grams (i.e. average catalyst exposure duration) of agent.

In moving-burden bed reactor, the residence time of catalyst can correspond to catalyst granules being averaged based on moving bed The length of the speed traveling bed time quantum required to outlet.For example, the flow that methanol flows into moving-burden bed reactor can correspond to 1.0hr^-1Air speed, it means that every gram of catalyst of 1 gram of methanol is per hour.In such an example, if be catalyzed in reactor The mean residence time of agent is 48 hours (average speed based on moving bed relative to the size of bed), then catalyst in moving bed Average catalyst exposure duration will be every gram of catalyst of 24 grams of methanol.Similarly, in terms of being related to fluidized bed, catalyst stops Stay the time that can determine based on catalyst is removed from reactor for regenerated rate.Catalyst residence times can correspond to The time quantum needed for the catalyst for removing the amount of weight for being equal to catalyst bed.Based on the residence time, can with movement The mode that the calculating of bed is similar calculates average catalyst exposure duration.

During partial regeneration, catalyst can be exposed to oxidation environment to remove coke from catalyst, but in portion Divide the net amount of coke of residual on a catalyst after regeneration that can be greater than 0.1 weight %.When carrying out partial regeneration, due to catalysis Remaining amount of coke in agent, effective average catalyst exposure duration of regenerated catalyst by be a non-zero value.Work as progress When partial regeneration, coke removal amount can be thick in a linear fashion with effective average catalyst exposure duration of partial regeneration catalyst It is slightly proportional.In this discussion and following claim, when partially regenerating catalyst, partial regeneration catalyst is averaged Catalyst exposure duration passes through remains in catalyst multiplied by partial regeneration for the average catalyst exposure duration before regeneration later On the weight % of coke determine.For example it is assumed that catalyst can have 100 grams of methanol/gram catalysts before being regenerated Exposure duration.In this example, partial regeneration is used to remove the coke of 60 weight % on catalyst.This means that in regeneration Afterwards, the coke of 40 weight % (or with fractional representation for 0.4) retains on a catalyst.In such an example, regenerated catalyst Average catalyst exposure duration be 0.4 × 100=40 grams of methanol/gram catalyst.

It, can be based on any catalyst recycle by the catalyst with non-zero initial values in terms of carrying out partial regeneration The fact that exposure duration, modifies the calculating of the average catalyst exposure duration of catalyst reactor.Above-mentioned identical calculating can For determining initial value.Then the non-zero catalyst exposure duration of regenerated catalyst can be added to initial value, to determine reaction Average catalyst exposure duration in device.In the above-described example, if the average catalyst exposure duration of partial regeneration catalyst It is every gram of catalyst of 10 grams of methanol, and is urged if the mean exposure measurement in reactor is 24 grams every gram of methanol calculated as above Agent, then the average catalyst exposure duration of system is every gram of catalyst of 34 grams of methanol when using partial regeneration.It should also infuse Meaning, instead of the catalyst of partial regeneration, a part of catalyst for introducing reactor can correspond to fresh supplement catalyst.? These aspect, introduce the catalyst of reactor catalyst exposure duration can be fresh makeup catalyst (zero exposure duration) and The weighted average of the catalyst exposure duration of partial regeneration catalyst.

For the catalyst comprising MFI skeleton zeolite, catalyst recirculation rate may depend on required product, generate about 1 Gram CH₃OH/ grams of catalyst is to about 2000 grams of CH₃The average catalyst exposure duration of the catalyst reactor of OH/ grams of catalyst/ The catalyst recirculation rate of averaging loop length may be suitable, or about 50 grams of CH₃OH/ grams of catalyst is to about 1000 grams CH₃OH/ grams of catalyst, or about 100 grams of CH₃OH/ grams of catalyst is to about 1500 grams of CH₃OH/ grams of catalyst, or about 100 grams of CH₃OH/ Gram catalyst is to about 1000 grams of CH₃OH/ grams of catalyst.Target average catalyst exposure duration may depend on the specificity of catalyst Matter and/or required product mixtures.In some aspects for needing shorter average catalyst exposure duration, average catalyst is sudden and violent The dew time can be about 1 gram of CH₃OH/ grams of catalyst is to about 200 grams of CH₃OH/ grams of catalyst, or about 5 grams of CH₃OH/ grams of catalyst is to about 150 grams of CH₃OH/ grams of catalyst, or about 1 gram of CH₃OH/ grams of catalyst is to about 100 grams of CH₃OH/ grams of catalyst.When needing longer Between other aspects, average catalyst exposure duration can be about 200 grams of CH₃OH/ grams of catalyst is to about 2000 grams of CH₃OH/ grams of catalysis Agent, or about 400 grams of CH₃OH/ grams of catalyst is to about 1500 grams of CH₃OH/ grams of catalyst, or about 500 grams of CH₃OH/ grams of catalyst is to about 1000 grams of CH₃OH/ grams of catalyst.Above-mentioned average catalyst exposure duration can be for example by taking out about 0.01 weight % to about 3.0 every 1 anti-violences of weight % catalyst are exposed to the methanol of gram reforming catalyst to realize, or about 0.01 weight % to about 1.5 weights Measure %, or about 0.1 weight % to about 3.0 weight %, or about 1.0 weight % to about 3.0 weight %.It should be noted that for example, if only Partial regeneration is carried out to the catalyst of taking-up, then can change these and take out rate.For urging in addition to MFI skeleton catalyst Agent can choose catalyst recirculation rate to generate average catalyst exposure duration of catalyst reactor/averagely follow Ring length is about 25 grams of CH₃OH/ grams of catalyst is to about 200 grams of CH₃OH/ grams of catalyst, or about 25 grams of CH₃OH/ grams of catalyst is to about 180 grams of CH₃OH/ grams of catalyst, or about 50 grams of CH₃OH/ grams of catalyst is to about 180 grams of CH₃OH/ grams of catalyst, or about 50 grams CH₃OH/ grams of catalyst is to about 150 grams of CH₃OH/ grams of catalyst, or about 25 grams of CH₃OH/ grams of catalyst is to about 100 grams of CH₃OH/ grams Catalyst, or about 50 grams of CH₃OH/ grams of catalyst is to about 100 grams of CH₃OH/ grams of catalyst, or about 100 grams of CH₃OH/ grams of catalyst is extremely About 180 grams of CH₃OH/ grams of catalyst, or about 100 grams of CH₃OH/ grams of catalyst is to about 150 grams of CH₃OH/ grams of catalyst.Including non-MFI The suitable length of the cycle of the catalyst of skeleton zeolite may depend on the type of zeolite.

It should be noted that oxygenate-containing feedstock and/or conversion reaction environment may include the water of various ratios.Oxygenate is converted into aromatic hydrocarbons Cause to produce water as product with alkene, so that oxygenate (such as methanol or dimethyl ether) and the relative quantity of water can be in reaction environments Interior variation.Based on temperature present in methanol conversion process, the water in reaction environment can lead to " decatize " of catalyst.Therefore, Catalyst for converting oxygenate in aromatic hydrocarbons is preferably kept substantially active catalyst in decatize.In contact zeolite Before catalyst, water be can also exist in charging.For example, the commercial processing in methanol is formed in gasoline, in order to control reaction Primary catalyst can be used by one in charging before contact zeolite catalyst is to form gasoline in heat release in device Methanol is divided to be converted into dimethyl ether and water.

Catalyst for oxygenate conversion

In all fields, the zeolite catalyst composition of transition metal enhancing can be used for converting oxygenate-containing feedstock in stone brain Oily boiling fraction and alkene.In the discussion and following claim, zeolite is defined as having by connecting by bridge joint oxygen atom The crystalline material of the porous skeleton structure of the Tetrahedral atoms building connect.The example of known zeolites skeleton is in " Atlas of Zeolite Frameworks”published on behalf of the Structure Commission of the International Zeolite Association”,6^th revised edition,Ch.Baerlocher, L.B.McCusker, D.H.Olson, eds., Elsevier, New York (2007) and corresponding websitehttp:// www.iza-structure.org/databases/In provide.Under this definition, zeolite can refer to zeolite framework type And the alumino-silicate of the crystal structure containing the heteroatomic oxide for being different from silicon and aluminium.This hetero atom may include usual The known any hetero atom being suitable for inclusion in zeolite skeleton, such as gallium, boron, germanium, phosphorus, zinc and/or can replace zeolite skeleton in Silicon and/or aluminium other transition metal.

Suitable zeolite may include 10 yuan or 12 member ring hole path networks, such as 1 10 member ring hole paths of dimension or 3 10 member rings of dimension Hole path.The example of suitable zeolite with three-dimensional 10 member ring hole path networks includes the zeolite with MFI or MEL skeleton, example Such as ZSM-5 or ZSM-11.ZSM-5 has a detailed description in United States Patent (USP) No.3,702,886 and Re.29,948.ZSM-11 is in beauty It is had a detailed description in state patent No.3,709,979.Preferably, zeolite is ZSM-5.Conjunction with 1 10 member ring hole path networks of dimension The example of suitable zeolite includes having MRE (ZSM-48), MTW, TON, the zeolite of MTT and/or MFS skeleton.In some respects, have The zeolite of three-dimensional hole path is preferably used for the conversion of methanol, such as the zeolite with MFI skeleton.

In general, the zeolite with required methanol conversion activity can have about 10 to about 200, or about 15 to about 100, or about 20 To about 80, or the silica alumina ratio of about 20 to about 40.For example, silica alumina ratio can be at least about 10, or at least about 20, or at least about 30, or at least about 40, or at least about 50, or at least about 60.Additionally or as selection, silica alumina ratio can be about 300 or lower, or About 200 or lower, or about 100 or lower, or about 80 or lower, or about 60 or lower, or about 50 or lower.

In general, the silica alumina ratio reduced in zeolite will lead to zeolite with higher acidity, therefore such as to hydrocarbon or hydrocarbon feed The cracking of petroleum feeding has higher activity.However, the conversion about oxygenate to aromatic hydrocarbons, this increased cracking activity can It can not be beneficial, but the formation that may cause residual carbon or coke during conversion reaction increases.This residual carbon can It is deposited on zeolite catalyst, catalyst is caused to inactivate at any time.Silica alumina ratio is at least about 40, for example, at least about 50 or at least About 60, the amount of the additional residual carbon formed due to the acidity of catalyst or cracking activity can be reduced or be minimized.

It should be noted that molar ratio as described herein is silica alumina ratio.If describing corresponding silica and aluminium oxide Than then since there are two aluminium atoms, silica (SiO in each aluminium oxide stoichiometry unit₂) and aluminium oxide (Al₂O₃) it is corresponding than that will be big twice.Therefore, it is 20 that silica alumina ratio, which is 10 ratios for corresponding to silica and aluminium oxide,.

In some respects, the zeolite in catalyst can at least partly exist with hydrogen form.Depending on for synthesizing boiling The condition of stone, this can correspond to convert zeolite from such as na form.This can easily be realized, for example, being handed over by ion Zeolite catalysts of changing commanders are ammonium form, and then the temperature lower calcination in air or inert atmosphere at about 400 DEG C to about 700 DEG C is with general Ammonium form is converted into activated hydrogen form.

Additionally or as selection, zeolite catalyst may include transition metal and/or be enhanced by transition metal.Preferably, mistake Crossing metal is the 12nd race's metal (sometimes referred to as Group IIB) from IUPAC periodic table, is selected from Zn, Cd or combinations thereof.More typically Ground, transition metal can be any convenient transition metal of the 6-15 race selected from IUPAC periodic table.Transition metal can lead to It crosses in any convenient method incorporation zeolite/catalyst, such as by dipping, ion exchange is ground before extrusion, and/or Pass through any other convenient method.Optionally, the transition metal mixed in zeolite/catalyst can correspond to two or more Kind metal.After dipping or ion exchange, transition metal enhancing catalyst can in air or inert atmosphere at about 400 DEG C extremely It is handled at a temperature of about 700 DEG C.The amount of transition metal be represented by metal phase for total catalyst weight (including any zeolite and Any adhesive) weight percent.Catalyst can include about one or more transition of 0.05 weight % to about 20 weight % Metal, or about 0.1 weight % to about 10 weight %, or about 0.1 weight % to about 5 weight %, or about 0.1 weight % to about 2.0 Weight %.For example, the amount of transition metal can be the transition metal of at least about 0.1 weight %, or at least about 0.25 weight % Transition metal, or at least about 0.5 weight %, or at least about 0.75 weight %, or at least about 1.0 weight %.Additionally or as choosing It selects, the amount of transition metal can be about 20 weight % or less, or about 10 weight % or less, or about 5 weight % or less, or About 2.0 weight % or less, or about 1.5 weight % or less, or about 1.2 weight % or less, or about 1.1 weight % or more It is few, or about 1.0 weight % or less.

In terms of some optional, zeolite catalyst can be substantially free of phosphorus.Catalyst combination substantially free of phosphorus Object can contain about 0.01 weight % or less phosphorus, such as the phosphorus of less than about 0.005 weight %, or less than about 0.001 weight % Phosphorus.Zeolite catalyst substantially free of phosphorus can be substantially free of the phosphorus added intentionally or substantially free of the phosphorus added intentionally And as phosphorus existing for the impurity in the reagent for being used to form carbon monoxide-olefin polymeric.In some respects, zeolite catalyst can be with Phosphorus without containing addition, such as without the phosphorus intentionally added and/or without phosphorus impurities to being used to characterize reagent and/or gained zeolite Standard method detectable limit in.

Optionally, for methanol conversion zeolite catalyst may include addition phosphorus, such as by dipping, ion exchange, The phosphorus of grinding or other convenient method additions before extrusion.The amount of phosphorus can be with the amount phase of transition metal in carbon monoxide-olefin polymeric It closes.In some respects, the molar ratio of phosphorus and transition metal can for 0.5 to 5.0 or 1.5 to 3.0 or 1.0 to 2.5 or 1.5 to 2.5.Phosphorus and transition metal it is mole relatively high when, phosphorus can be conducive to the virtue to keep relative stability in oxygenate method for transformation Hydrocarbon forms selectivity.Additionally or as selection, catalyst can include about the phosphorus of 0.05 weight % to about 10 weight %, or about 0.1 Weight % to about 10 weight %, or about 0.1 weight % to about 5 weight %, or about 0.1 weight % to about 2.0 weight %.For example, The amount of phosphorus can be at least about 0.1 weight %, or at least about 0.25 weight %, or at least about 0.5 weight %, or at least about 0.75 Weight %, or at least about 1.0 weight %.Additionally or as selection, the amount of phosphorus can be about 10 weight % or less, or about 5 weights % or less, or about 2.0 weight % or less, or about 1.5 weight % or less, or about 1.2 weight % or less are measured, or about 1.1 weight % or less, or about 1.0 weight % or less.

Carbon monoxide-olefin polymeric can use its initial crystalline form or be configured to catalyst granules (such as passing through extrusion) The zeolite of transition metal enhancing afterwards.The method for preparing zeolite extrudate in the case where adhesive is not present is disclosed in for example beautiful State patent No.4, in 582,815, entire contents are incorporated herein by reference.It preferably, can be to prepare zeolite (such as logical Cross extrusion) mix transition metal later to form autoadhesion catalyst granules.Optionally, autoadhesion catalyst can vapour after the extrusion It steams.Term " non-adhering " and " autoadhesion " be it is synonymous and mean this carbon monoxide-olefin polymeric without usually with zeolite catalyst group It closes to enhance any inorganic oxide adhesive of its physical property, such as aluminium oxide or silica.

The zeolite catalyst composition of transition metal enhancing used herein is also based on the activity or α of hexane cracking Value characterizes.α value is the measurement of the acid activity of zeolite catalyst, compared with standard silica-aluminium oxide catalyst.Alpha test It is described in United States Patent (USP) 3,354,078；Journal of Catalysis,Vol.4,p.527(1965)；Vol.6,p.278 (1966)；And Vol.61 p.395 in (1980), is respectively incorporated herein by reference the description.Survey used herein The experiment condition of examination include about 538 DEG C steady temperature and variable flow velocity, such as Journal of Catalysis, Vol61, P.395 it is described in detail in.Higher α value corresponds to more active Cracking catalyst.For oxygenate reforming catalyst, α It may be that suitably, preferably α value is greater than 100 that value, which is at least 15,.Particularly, α value can be about 15 to about 1000, or about 50 to about 1000, or about 100 to about 1000.

As the alternative solution for forming autoadhesion catalyst, zeolite crystal can form bonding catalysis in conjunction with adhesive Agent.Proper adhesive for zeolite based catalysts may include various inorganic oxides, such as silica, aluminium oxide, oxidation Zirconium, titanium dioxide, silica-alumina, cerium oxide, magnesia, yttrium oxide or combinations thereof.For the catalysis comprising adhesive Agent, catalyst may include the zeolite of at least about 10 weight %, or at least about 30 weight %, or at least about 50 weight %, such as up to About 90 weight % or higher.In general, adhesive can with the about 1 weight % to about 90 weight % of carbon monoxide-olefin polymeric, for example, about 5 The amount of weight % to about 40 weight % exists.In some respects, catalyst may include the adhesive of at least about 5 weight %, such as extremely Few about 10 weight %, or at least about 20 weight %.Additionally or as selection, it is viscous that catalyst can include about 90 weight % or less Mixture, such as from about 50 weight % or less, or about 40 weight % or less, or about 35 weight % or less.For example, passing through grinding boiling Then mixture is extruded into catalyst pellets, zeolite and adhesive usually may be implemented by the aqueous mixture of stone and adhesive Combination.Such as United States Patent (USP) No.4,582,815 is disclosed in using the method for silica binder production zeolite extrudate In.Optionally, bonding catalyst can decatize after the extrusion.

In some respects, the adhesive for being substantially free of aluminium oxide can be used, such as viscous substantially free of aluminium oxide Mixture.In the present specification, the adhesive for being substantially free of aluminium oxide is defined as containing about 10 weight % or less, and for example, about 7 Weight % or less, or about 5 weight % or less, or the adhesive of about 3 weight % or less aluminium oxide.Substantially free of oxygen The adhesive for changing aluminium is defined as containing about 1 weight % or less, for example, about 0.5 weight % or less, or about 0.1 weight % or more Few adhesive.In other respects, it can be used without the aluminium oxide intentionally added and/or be not contained in for measuring adhesive And/or the adhesive of the aluminium oxide in the conventional detection limit of the composition of the reagent of formation adhesive.Although aluminium oxide is usually used Make the adhesive of zeolite catalyst, partially due to being easy to prepare the catalyst of aluminium oxide bonding, but in some aspects, in adhesive The activity that the presence of aluminium oxide can reduce or the zeolite of transition metal enhancing is inhibited to convert methanol into aromatic hydrocarbons.For example, for Bonding catalyst (such as passing through extrusion) is prepared later for the catalyst in transition metal incorporation catalyst, and transition metal can phase There is affinity to exposed oxidation aluminium surface for exposed zeolite surface, lead to embryo deposit increase and/or transition metal The bonding catalyst region with oxidation aluminium surface is moved to, the region with zeolite surface is conducive to.Additionally or as selection, The catalyst of aluminium oxide bonding can tend to the micro pore surface area for having low, it means that can be used for receiving the available of transition metal The amount of zeolite surface may be undesirable low.

As the example for forming bonding catalyst, following procedure describes the ZSM-5 catalyst to form silicabound The exemplary process of particle.It can be by ZSM-5 crystal and silica binder (such as Ultrasil silica binder) It is added in mixer and grinds.Additional deionized water can be added during grinding to be contained with the required solid for obtaining for extrusion Amount.Optionally, caustic solution can also be added in mixture and is ground.Then mixture can be extruded into required shape, Such as 1/10 " quatrefoil.Extrudate can be dried overnight under about 250 °F (121 DEG C), then at about 1000 °F (538 in nitrogen DEG C) under calcine about 3 hours.Then extrudate can be exchanged twice with about 1N ammonium nitrate solution.The crystal of exchange can be about It is dried overnight under 250 °F (121 DEG C), is then calcined under about 1000 °F (538 DEG C) about 3 hours in air.This leads to dioxy The catalyst of SiClx bonding.Based on ammonium nitrate exchange and then aerial calcining, in this bonding catalyst ZSM-5 crystal can correspond to exchange the ZSM-5 that position has main hydrogen atom in zeolite intermediate ion.Therefore, this bonding catalysis Agent is sometimes be described as the bonding catalyst comprising H-ZSM-5.

For formed transition metal enhancing catalyst, bonding catalyst can via with containing for dipping required metal such as The solution initial wetting of Zn or P and impregnate.Then the crystal impregnated can be dried overnight under about 250 °F (121 DEG C), then be existed It is calcined under about 1000 °F (538 DEG C) about 3 hours in air.More generally, transition metal can what in office convenient time such as Mixed before or after ion exchange to form H-shaped formula crystal in zeolite catalyst, or formed bond extrudate before or Later.From the viewpoint of from the manufacture for promoting bound zeolite catalyst, in preferred some aspects, by squeezing out or other Convenient method is formed after bonding catalyst, transition metal can be mixed in bonding catalyst (such as by dipping or from Son exchange).

Reaction system configuration example

Fig. 1 shows the example for carrying out oxygenate conversion to form the reaction system configuration of naphtha boiling-range product. Notice for convenience, reactor shown in Fig. 1 be portrayed as fixed bed, downflow reactor (such as trickle bed reaction Device).It should be understood that it is moving-burden bed reactor and/or stream that any or all reactor shown in Fig. 1, which all can serve as selection, Fluidized bed reactor.In Fig. 1, charging 105 can correspond to the charging of containing oxygenates.In particular instances, charging 105 can correspond to In 96 weight % methanol and 4 weight % water.Second charging 106 can correspond to olefin-containing charging.It is optionally possible to by oxygenate into Material 105 introduces reactor as multiple inlet flows, for example, the mixture containing first alcohol and water the first inlet flow and containing nitrogen and Second inlet flow of the mixture of hydrogen.Optionally, oxygenate-containing feedstock 105 and olefin feedstocks 106 can enter reactor 110 it Preceding combination.

It is anti-that 105 (or combinations of oxygenate-containing feedstock 105 and olefin feedstocks 106) introducing initial dewatering will optionally be fed Answer device 110.Initial dewatering reactor 110 may include acidic catalyst, such as acidic oxidation Al catalysts, can promote methanol, Balanced reaction between water and dimethyl ether.This can cause to generate the effluent 115 comprising methanol and dimethyl ether.Art technology It will be recognized that when carrying out oxygenate conversion, dimethyl ether and methanol can usually use personnel in a similar way.Methanol It is high exothermic heat that dehydration, which forms dimethyl ether,.By progress initial dewatering, the heat generated in conversion reactor can be reduced, this The temperature control in conversion reactor can be improved.Optionally, a part of oxygenate-containing feedstock 105 can be around dehydration reactor simultaneously And conversion reactor 120 can be directly inputted.In other oxygenates such as C₂₊Alcohol or bigger ether are used as the aspect of charging, can save Slightly dehydration reactor, so that 105 (or combinations of oxygenate-containing feedstock 105 and olefin feedstocks 106) of charging are conversion reactors 120 Inlet flow.

Then oxygenate-containing feedstock 105 and olefin feedstocks 106 (and/or effluent 115 containing dimethyl ether and methanol) are sent Enter conversion reactor 120.The input of conversion reactor 120 can be exposed under conditions effective to being formed and converting effluent 125 Reforming catalyst.Then conversion effluent 125 can be separated, such as by using 3 phase separators 130.It is generated by separator 130 A phase can be water phase 133, it includes conversion effluent 125 present in overwhelming majority water.It is generated by separator 130 Another phase can correspond to hydrocarbon liquid product 137.Hydrocarbon liquid product can correspond to the stone brain formed during conversion reaction Oily boiling range compound.Optionally, hydrocarbon liquid product may include a part of hydrocarbon compound, it includes one or more hetero atoms, Such as oxygen, sulphur, nitrogen and/or other hetero atoms being typically found in petroleum or biologically-derived charging.

Hydrocarbon gas product 135 can correspond to by the third phase that separator 130 generates.Hydrocarbon gas product 135 may include C corresponding to light paraffins and light olefin_4-Compound.Optionally, the recycle sections 122 of hydrocarbon gas product 135 can be with A part as inlet flow is recycled to conversion reactor 120.In the sufficiently large some configurations of the amount of recycle sections 122 In, there may also be discharges or waste stream (not shown) with by C in conversion reactor 120_4-The accumulation of alkane reduces or minimum Change.

Embodiment 1 carries out methanol conversion using zeolite catalyst

Various reforming catalysts are tested in isothermal fixed bed reactors without recycling.In this embodiment, it feeds It is equivalent to 100 weight % methanol.It will feed in 450 DEG C of temperature, the pressure of 15psig and 2hr^-1Weight (hourly) space velocity (WHSV) under be exposed to Reforming catalyst.

The ZSM-5 reforming catalyst used in this embodiment is based on small crystals, autoadhesion MFI skeleton (ZSM-5) zeolite. The silica alumina ratio of ZSM-5 is 20-40, and α value is at least 100.For adding the catalyst of Zn, squeezed in the H- type for preparing autoadhesion zeolite Out after object, pass through Zn (NO₃)₂Water retting add Zn.

Fig. 2 shows the pass of the aromatics yield of methanol charging conversion and the inlet amount of various types zeolite catalyst processing System.Catalyst includes autoadhesion ZSM-48；Yttrium oxide bonds ZSM-48 (ratio of zeolite and adhesive is 65:35)；Aluminium oxide is viscous Close ITQ-13 (ratio of zeolite and adhesive is 65:35)；Autoadhesion ZSM-5；Oneself of 0.5 weight %Zn is loaded on a catalyst Bond ZSM-5.ZSM-5 catalyst is similar to catalyst used in embodiment 1.As shown in Fig. 2, for all zeolite catalysises Agent, the aromatic hydrocarbons of every kind of catalyst form selectivity and start in initial level, are processed and stablize then as a greater amount of chargings Decline.Fig. 2, which is also shown, to be added 0.5 weight %Zn into catalyst and can be improved the initial level of arenes selectivity, but sudden and violent The decline of arenes selectivity is kept similar when being exposed to charging.

The zeolite catalyst conversion methanol and alkene of the loaded transition metal of embodiment 2- apparatus

It is impregnated by incipient wetness with zinc nitrate similar to the autoadhesion ZSM-5 catalyst of the catalyst in embodiment 1 To form 1 weight %Zn/ZSM-5 catalyst.As shown in Fig. 2, Zn is added into zeolite catalyst can improve the first of catalyst Beginning arenes selectivity.1 weight %Zn/ZSM-5 catalyst is exposed in two kinds of charging to determine in metal promoted The influence of alkene is added in the presence of zeolite catalyst.Similar to embodiment 1, first kind charging is equivalent to 100 weight % methanol.The The charging of two classes is equivalent to about 70 weight % methanol and about 30 weight %1- amylenes.It is about that this, which is equivalent to oxygenate and olefin molar ratio, 5 charging.In this embodiment, charging is in isothermal reactor in 450 DEG C of temperature, the pressure of 90psig and 2hr^-1It is heavy when Reforming catalyst is exposed under air speed.Data shown in Fig. 3 correspond to every kind of charging and are exposed to after catalyst 46 hours or about The data of every gram of catalyst of 90 grams of chargings.

Fig. 3 shows the product distribution of the hydrocarbon products generated by methanol and methanol/1- amylene feedstocks conversion.Base in charging All methanol and/or dimethyl ether convert under these conditions in sheet.Due on zeolite catalyst there are the Zn of 1 weight %, The conversion of methanol charging results in oxycarbide (CO, the CO of at least about 15 weight % (relative to total hydrocarbon products)₂) and methane. On the contrary, there is the charging comprising alkene and methanol the oxycarbide less than 4 weight % to add methane yield.When use methanol and alkene Mixed feeding when this substantially reduce of the amount of methane and oxycarbide that generates lead to aromatic production (i.e. arenes selectivity) Increase accordingly.Although the ratio of the ratio or aromatic hydrocarbons and alkene of aromatic hydrocarbons and alkane when adding olefin feedstocks using compound oxygenate seemingly Do not change, but the ability for avoiding the formation of methane and oxycarbide seems that arenes selectivity is made to improve 5% or more (relatively always Hydrocarbon yield).Therefore, compared with the arenes selectivity of charging for only including oxygenate, it appears that use the combination of oxygenate and alkene Charging provides unexpected transfer to the arenes selectivity of the reforming catalyst comprising carried metal.

Embodiment 3- converts methanol and alkene with zeolite catalyst (no metal)

It further studies and is exposed in the case where not other carried metal using autoadhesion ZSM-5 catalyst To the decline of the selectivity of oxycarbide and methane when charging.In isothermal reactor, in the stagnation pressure of 15psig (~100kPag) Power and 2hr^-1Air speed under, processing is equivalent to the chargings of 100 weight % methanol under autoadhesion ZSM-5 catalyst action.Conversion Temperature is 325 DEG C, 350 DEG C or 375 DEG C.Fig. 4 shows that methanol charging converts under reforming catalyst effect at three temperature Result.As shown in figure 4, the initial part of conversion reaction carries out at 350 DEG C, 325 DEG C are then down to, then rises to temperature 375℃。

Fig. 4 show by gas chromatography measure with always conversion hydrocarbon yield compared with alkane, aromatic hydrocarbons, alkene and The yield advantage of " other ".It is similar with Fig. 2, ZSM-5 catalyst to the selectivity of aromatic hydrocarbons since initial higher level, then Decline with the increase of charging exposure.This trend is at 350 DEG C as it can be seen that and the recovery when conversion temperature is restored to 375 DEG C. Although in addition, at 325 DEG C it can be seen that arenes selectivity reduce trend, at such a temperature aromatic hydrocarbons formed selectivity into One step is changed into lower value.This is considered as since most of (unconverted) methanol and/or dimethyl ether are present in total hydrocarbon and produce In object.In other words, the methanol/dimethyl ether for being converted at 325 DEG C, it is believed that selectivity remains unchanged, but deposits in total hydrocarbon products Mean aromatics yield reduction in a large amount of unconverted methanol/dimethyl ethers.

Fig. 5 is shown to carry out similar to conversion reaction as a result, but charging includes about 70 weight % first using ZSM-5 catalyst Alcohol and about 30 weight %1- amylenes (adding olefin feedstocks similar to oxygenate used in embodiment 2).With the methanol in Fig. 5 into Material converts methanol/1- amylene feedstocks of combination under the same conditions, including uses 350 DEG C, followed by 325 DEG C, followed by 375 DEG C Conversion temperature sequence.As shown in figure 5, addition 1- amylene reduces or minimizes the difference of arenes selectivity at 325 DEG C.However, Relative to the arenes selectivity of methanol charging, addition 1- amylene seems not influence total aromatic selective at 350 DEG C or 375 DEG C Property.Therefore, for the zeolite catalyst of not carried metal, be added into charging alkene seem will not it is sufficiently high with allow into Change total arenes selectivity at a temperature of oxygenate converts completely in material.

It is without being bound to any particular theory, it is believed that other than being converted, the alkene in charging be can also contribute to The conversion of oxygenate in charging.This is shown in FIG. 6, Fig. 6 show in Figure 4 and 5 conversion operation hydrocarbon products (including " product " corresponding to unreacted methanol/dimethyl ether) distribution.In Fig. 6, the left-hand bar of every kind of product types corresponds to first Alcohol charging, and right side item corresponds to methanol and adds olefin feedstocks.It is urged as shown in fig. 6, methanol charging is exposed to conversion at 325 DEG C Agent generates a large amount of unconverted methanol/dimethyl ethers.In contrast, for the charging comprising methanol and 1- amylene, only seldom The methanol of amount is unconverted.

Fig. 7 shows the conversion reaction corresponding to Figure 4 and 5 in each temperature (325 DEG C, 350 DEG C and 375 DEG C) studied Under product yield other details.Fig. 7 includes the data that methanol charging and mixing methanol add 1- amylene feedstocks.For in Fig. 7 Shown in every kind of product types (water, C₅+、C₃-C₄、C₁-C₂), three, left side item is fed corresponding to methanol, and three, right side item pair Olefin feedstocks should be added in methanol.Three items of each series from left to right correspond to 325 DEG C, 350 DEG C and 375 DEG C.For in Fig. 7 Yield, any unreacted methanol/dimethyl ether do not include yield calculate a part in.As shown in fig. 7, being fed to methanol Middle addition alkene leads to less amount of C₁And/or C₂It generates (such as generation of methane).The discharge reduction of generation, but this at least portion Divide ground by the reduction of oxygenate in charging to explain.Similarly, the obviously increasing for alkene of the charging comprising methanol and alkene can It can be related with alkene additional present in charging.

Embodiment 4- reduces durene and is formed

Fig. 8 is shown about during using the charging of ZSM-5 catalyst (no metal) conversion methanol and methanol/1- amylene feedstocks The other details of the aromatic hydrocarbon type of generation.The result in Fig. 8 is obtained under the reaction condition listed in conjunction with Figure 4 and 5.In fig. 8, " A6 " corresponds to the aromatic compound (i.e. benzene) comprising 6 carbon atoms.In other words, " A6 " refers to C₆Aromatic compound.Think " A7 ", " A8 " and " A9 " column correspond to various alkyl-substituted benzene." A10 " and " A11 " column may include alkyl-substituted benzene, naphthalene and Substituted naphthalene.For every kind of product type shown in fig. 8, three, left side item is fed corresponding to methanol, and three, right side item pair Olefin feedstocks should be added in methanol.Three items of each series from left to right correspond to 325 DEG C, 350 DEG C and 375 DEG C.Such as Fig. 8 institute Show, alkene, which is added, into methanol charging causes the amount of the durene generated under all temperature (325 DEG C, 350 DEG C, 375 DEG C) significant It reduces.Durene corresponds to 1,2,4,5- durols, therefore represents the aromatic hydrocarbons of substantial portion present in " A10 " aromatic hydrocarbons column.Du Alkene is a kind of compound that can be crystallized at a lower temperature, may will affect gasoline energy and appearance.Keeping similar aromatic hydrocarbons The ability for inhibiting durene to be formed while forming overall selectivity is that oxygenate and the combined feed of alkene is used to feed as conversion Another unexpected advantage.

Fig. 9 is shown when carrying out the conversion of methanol/1- amylene feedstocks using 1 weight %Zn/ZSM-5 catalyst, is realized The similar reduction that durene is formed.By in isothermal reactor in 450 DEG C of temperature, the pressure of 90psig and 2hr^-1WHSV under Methanol charging or methanol/1- amylene feedstocks are converted to generate result shown in Fig. 9.In Fig. 9, the left-hand bar of every kind of product types Corresponding to methanol plus olefin feedstocks, and right side item is fed corresponding to methanol.It should be noted that the temperature for the result in Fig. 9 increases Additionally aid the yield for reducing durene.However, the benefit for being reduced durene yield using combined oxygenate/olefin feedstocks is being schemed It is still apparent in 9.Based on Fig. 9, adding alkene when carrying out oxygenate conversion can permit to form conversion effluent, wrap Containing C of the total weight less than 10 weight % relative to hydrocarbon in conversion effluent₁₀Aromatic hydrocarbons.Additionally or as selection, it is less than 10 weights Measure the C of %₁₀Aromatic hydrocarbons (or less than 5 weight %) can correspond to durene.

Embodiment 5- uses the conversion of non-MFI zeolite catalyst

In embodiment 1 as the result is shown for converting oxygenate to the non-MFI zeolite catalyst of alkene and/or aromatic hydrocarbons The relatively short processing service life.Particularly, increase as exposure to the amount of the oxygenate of catalyst, such as more than about 100 grams oxygen close Every gram of catalyst of object, non-MFI catalyst decline rapidly the selectivity that oxygenate converts.Unexpectedly, it has been found that using Combined oxygenate and olefin feedstocks can reduce or minimize this decline of the activity of conversion of non-MFI zeolite catalyst.

Figure 10 shows the conversion results of the methanol charging (similar to the charging in embodiment 1) of ZSM-48 catalyst. ZSM-48 catalyst does not include the additional metal of load on a catalyst.Conversion reaction in isothermal reactor 350 DEG C, 15psig (~100kPag) and about 2hr^-1WHSV under carry out.It is also used using the similar conversion reaction of ZSM-48 catalyst upper Methanol/1- the amylene feedstocks for stating combination carry out.Combined methanol/1- amylene feedstocks conversion results are shown in Figure 11.

Figure 10 is seemed to indicate that, when being fed using methanol, it is due to converting first that most alkene, which forms selectivity loss, The capacity loss of alcohol charging.For example, the amount of unconverted methanol be equivalent under the only exposure of every gram of catalyst of 100 grams of methanol into About 20 weight % of material.On the contrary, Figure 11 shows that the feedstock conversion of at least 90 weight % is protected when alkene exists in charging Hold the exposure that every gram of catalyst is fed until at least 150 grams.Based on extrapolation, further apparently, about 90 weight % can be kept Feedstock conversion, until at least 200 grams feed every gram of catalyst exposure., it is surprising that the aromatic hydrocarbons in Figure 10 and 11 It is similar that selectivity, which looks, even if Figure 10 shows the combined feed conversion ratio of substantially relatively low amount.Therefore, for non- MFI zeolite catalyst, in oxygenate-containing feedstock comprising alkene seem by allow increase charging be converted into alkene and provide it is beneficial Effect, while keeping the somewhat similar selectivity formed to aromatic hydrocarbons.Based on the data in Figure 11, addition alkene, which can permit, to be turned Change the average catalyst that reactor is fed at about 50 grams between every gram of catalyst of every gram of catalyst and about 200 grams of chargings to be exposed to Feed operation, (or about 50 grams to about 150 grams, or about 75 grams to about 200 grams, or about 75 grams to about 175 grams, or about 75 grams to about 150 grams, or about 100 grams to about 200 grams), while still keeping the oxygenate conversion of at least 85 weight % in charging, or at least 90 weights Measure %.In other words, convert oxygenate in effluent can the total hydrocarbon products of Zhan 15 weight % or less or 10 weight % or more It is few.

Additional embodiment

The method of the formation naphtha composition of embodiment 1., comprising: by the charging comprising oxygenate and alkene about 300 Average reaction temperature, the gross pressure of about 10psig (~70kPag) to about 400psig (~2700kPag) DEG C to about 550 DEG C, And 0.1hr^-1To 20.0hr^-1WHSV under be exposed to reforming catalyst to form conversion effluent, conversion effluent includes octane The naphtha boiling-range fraction that value is at least 80, conversion effluent is further included is relative to the total weight of hydrocarbon in conversion effluent Less than CO, CO of 6.0 weight %₂And CH₄Combination, feed have about 1 to about 20 oxygenate and olefin molar ratio, transfer Changing catalyst includes that at least zeolite with MFI skeleton structure of 10 weight %, zeolite has the sial of 10-200 (or 20-40) Than the α value at least 5 (or at least 15), reforming catalyst further includes 0.1 weight % and is supported on conversion to 3.0 weight % Transition metal on catalyst.

The method of 2. embodiment 1 of embodiment, wherein naphtha boiling-range fraction includes at least 90 (or at least 93, or extremely Few octane number 97) and the weight relative to naphtha boiling-range fraction are at least about aromatic hydrocarbons of 40 weight %.

The method of any of above embodiment of embodiment 3., wherein average reaction temperature is at least about 400 DEG C, or at least About 450 DEG C.

The method of any of above embodiment of embodiment 4., wherein oxygenate includes methanol, and reforming catalyst includes 1 gram To the average catalyst exposure duration of every gram of catalyst of 2000 grams of oxygenates or 1 gram to 200 grams or 400 grams to 1500 grams.

The method of the formation naphtha composition of embodiment 5., comprising: by the charging comprising oxygenate and alkene about 300 DEG C to about 550 DEG C of average reaction temperature, the gross pressure of about 10psig (~70kPag) to about 400psig (~2700kPag), And 0.1hr^-1To 20.0hr^-1WHSV under be exposed to reforming catalyst with formed include naphtha boiling-range fraction conversion flow out Object, conversion effluent also include the total weight of hydrocarbon in the effluent relative to conversion for at least about alkene of 30 weight % and are less than The oxygenate of 15 weight % feeds the oxygenate and olefin molar ratio with 1 to 20, and wherein reforming catalyst includes at least 10 weights Measure 10 member rings or 12 yuan of boilings with the skeleton structure for being different from MFI (being optionally different from MFI or MEL) skeleton structure of % Stone, zeolite have the silica alumina ratio of 10 to 200 (or 20 to 40) and the α value of at least 5 (or at least 15), and reforming catalyst further wraps The average catalyst exposure duration of every gram of catalyst containing 25 grams to 200 grams oxygenates, reforming catalyst optionally also include 0.1 weight Measure the transition metal (preferably Zn) of % to 3.0 weight % being supported on reforming catalyst.

The method of 6. embodiment 5 of embodiment, wherein oxygenate includes methanol or in which reforming catalyst includes 50 grams To the average catalyst exposure duration of every gram of catalyst of 200 grams of methanol, (or 25 grams to 180 grams or 50 grams to 180 grams or 50 grams To 150 grams or 100 grams to 200 grams)；Or combinations thereof.

The method of 7. embodiment 5 or 6 of embodiment, wherein reforming catalyst includes at least 10 weight % with MRE (ZSM-48), the zeolite of the skeleton structure of MTW, TON, MTT, MFS or combinations thereof.

The method of any one of 8. embodiment 5 to 7 of embodiment, wherein the charging comprising oxygenate is exposed to conversion Catalyst includes that the charging comprising oxygenate is exposed to conversion in fluidized bed, moving bed, riser reactor or combinations thereof Catalyst, reforming catalyst take out and to be equivalent to the 0.3 weight % to 3.0 of oxygenate that every 1 anti-violence is exposed to gram reforming catalyst The rate of weight % catalyst regeneration regenerates (optional 1.5 weight % to 3.0 weight %).

The method of any one of 9. the embodiment above of embodiment, wherein the transition gold of 0.1 weight % to 3.0 weight % Belong to the Zn of Zn or 0.5 weight % to 1.5 weight % comprising 0.1 weight % to 3.0 weight %.

The method of any one of 10. the embodiment above of embodiment, wherein reforming catalyst also includes to be supported on conversion Phosphorus on catalyst, the molar ratio of phosphorus and zinc is optionally 1.5 to 3.0 on reforming catalyst.

The method of any one of 11. the embodiment above of embodiment, wherein charging includes 10 or lower or 6.0 or more Low oxygenate and olefin molar ratio.

The method of any one of 12. the embodiment above of embodiment, wherein the charging comprising oxygenate and alkene includes The first raw material containing at least part oxygenate and the second raw material containing at least part alkene, the first raw material and the second original Material mixes after entering the reactor containing reforming catalyst.

The method of any one of 13. the embodiment above of embodiment, a) wherein charging includes about 30 weight % to about 95 The oxygenate of weight %, the alkene of about 5 weight % to about 40 weight %, or combinations thereof；B) wherein charging includes at least about 20 weights Measure the component different from oxygenate and alkene of % to about 60 weight %, or about 40 weight % to 60 weight %；Or c) a) and b) Combination.

14. oxygenate of embodiment converts effluent, is at least 40 comprising the total weight relative to hydrocarbon in conversion effluent The aromatic hydrocarbons of weight %, less than CO, CO of 6.0 weight %₂And CH₄Combination, and less than 10 weight %% alkene, convert effluent Naphtha boiling-range part have at least 90 octane number, wherein the aromatic hydrocarbons packet relative to the total weight of aromatic hydrocarbons less than 10 weight % Containing C₁₀Aromatic hydrocarbons, wherein relative to C₁₀C of the total weight of aromatic hydrocarbons less than 10 weight %₁₀Aromatic hydrocarbons includes durene.

The oxygenate of 15. embodiment 14 of embodiment converts effluent, and wherein oxygenate conversion effluent includes to be less than CO, CO of 5.0 weight %₂And CH₄Combination, or in which relative to C₁₀C of the total weight of aromatic hydrocarbons less than 5 weight %₁₀Aromatic hydrocarbons packet Containing durene, or combinations thereof.

The conversion effluent that embodiment 16. is prepared according to any one of embodiment 1-13.

Although describe and illustrating the present invention by reference to particular implementation division, those of ordinary skill in the art will be managed Solution, the present invention are suitable for the modification being not necessarily shown here.It therefore, should be only with reference to institute in order to determine true scope of the invention Attached claims.

Claims

1. the method for forming naphtha composition, comprising: by the charging comprising oxygenate and alkene at about 300 DEG C to about 550 DEG C Average reaction temperature, the gross pressure and 0.1hr of about 10psig (~70kPag) to about 400psig (~2700kPag)^-1Extremely 20.0hr^-1WHSV under be exposed to reforming catalyst with formed include octane number be at least 80 naphtha boiling-range fraction conversion Effluent, conversion effluent further include relative to the total weight of hydrocarbon in conversion effluent be CO less than 6.0 weight %, CO₂And CH₄Combination, feed have about 1 to about 20 oxygenate and olefin molar ratio, wherein reforming catalyst include at least 10 The zeolite with MFI skeleton structure of weight %, zeolite have the silica alumina ratio and at least 5 of 10 to 200 (or 20 to 40) (or at least 15) α value, reforming catalyst also include the transition metal that is supported on reforming catalyst on of the 0.1 weight % to 3.0 weight %.

2. the method according to claim 1, wherein naphtha boiling-range fraction includes at least 90 (or at least 93, or at least 97) pungent Alkane value and weight relative to naphtha boiling-range fraction are at least about aromatic hydrocarbons of 40 weight %.

3. wherein average reaction temperature is at least about 400 DEG C, or at least about according to the method for any one of the claims 450℃。

4. according to the method for any one of the claims, wherein oxygenate includes methanol, reforming catalyst include 1 gram extremely The average catalyst exposure duration of every gram of catalyst of 2000 grams of oxygenates or 1 gram to 200 grams or 400 grams to 1500 grams.

5. the method for forming naphtha composition, comprising: by the charging containing oxygenate and alkene at about 300 DEG C to about 550 DEG C Average reaction temperature, the gross pressure and 0.1hr of about 10psig (~70kPag) to about 400psig (~2700kPag)^-1Extremely 20.0hr^-1WHSV under be exposed to reforming catalyst to form the conversion effluent comprising naphtha boiling-range fraction, conversion outflow Object also includes the oxygen relative to the total weight for converting hydrocarbon in effluent for at least about alkene of 30 weight % and less than 15 weight % Object is closed, the oxygenate and olefin molar ratio with 1 to 20 are fed, wherein reforming catalyst includes having not at least 10 weight % 10 member rings or 12 yuan of zeolites of the skeleton structure of MFI (being optionally different from MFI or MEL) skeleton structure are same as, zeolite has 10 To the α value of the silica alumina ratio of 200 (or 20 to 40) and at least 5 (or at least 15), reforming catalyst also includes that 25 grams to 200 grams oxygen close The average catalyst exposure duration of every gram of catalyst of object, reforming catalyst is optionally also comprising 0.1 weight % to 3.0 weight %'s The transition metal (preferably Zn) being supported on reforming catalyst.

6. method according to claim 5, wherein oxygenate includes methanol or in which reforming catalyst includes 50 grams to 200 grams Every gram of catalyst of methanol average catalyst exposure duration (or 25 grams to 180 grams or 50 grams to 180 grams or 50 grams to 150 grams, Or 100 grams to 200 grams)；Or combinations thereof.

7. according to the method for claim 5 or 6, wherein reforming catalyst include the having of at least 10 weight % MRE (ZSM-48), The zeolite of the skeleton structure of MTW, TON, MTT, MFS or combinations thereof.

8. according to the method for any one of claim 5 to 7, wherein the charging comprising oxygenate is exposed to reforming catalyst packet It includes and the charging comprising oxygenate is exposed to reforming catalyst in fluidized bed, moving bed, riser reactor or combinations thereof, turn Change catalyst and take out and be exposed to the 0.3 weight % of oxygenate to 3.0 weight % of gram reforming catalyst to be equivalent to every 1 anti-violence and is catalyzed The regenerated rate of agent regenerates (optional 1.5 weight % to 3.0 weight %).

9. according to the method for any one of the claims, wherein the transition metal of 0.1 weight % to 3.0 weight % include The Zn of the Zn or 0.5 weight % to 1.5 weight % of 0.1 weight % to 3.0 weight %.

10. wherein reforming catalyst also includes and is supported on reforming catalyst according to the method for any one of the claims Phosphorus, the molar ratio of phosphorus and zinc is optionally 1.5 to 3.0 on reforming catalyst.

11. according to the method for any one of the claims, wherein charging is closed comprising 10 or lower or 6.0 or lower oxygen Object and olefin molar ratio.

12. according to the method for any one of the claims, wherein the charging comprising oxygenate and alkene includes containing at least First raw material of a part of oxygenate and the second raw material containing at least part alkene, the first raw material and the second raw material are entering It is combined after reactor containing reforming catalyst.

13. a) wherein charging includes about 30 weight % to about 95 weight %'s according to the method for any one of the claims Oxygenate, the alkene of about 5 weight % to about 40 weight %, or combinations thereof；B) wherein charging includes at least about 20 weight % to about The component different from oxygenate and alkene of 60 weight %, or about 40 weight % to 60 weight %；Or c) combination a) and b).

14. oxygenate converts effluent, the aromatic hydrocarbons for being at least 40 weight % comprising the total weight relative to hydrocarbon in conversion effluent, Less than CO, CO of 6.0 weight %₂And CH₄Combination, and the alkene less than 10 weight % converts the naphtha boiling-range portion of effluent Divide the octane number at least 90, wherein aromatic hydrocarbons of the total weight relative to aromatic hydrocarbons less than 10 weight % includes C₁₀Aromatic hydrocarbons, wherein Relative to C₁₀C of the total weight of aromatic hydrocarbons less than 10 weight %₁₀Aromatic hydrocarbons includes durene.

15. oxygenate according to claim 14 converts effluent, wherein oxygenate conversion effluent includes less than 5.0 weight % CO, CO₂And CH₄Combination, or in which relative to C₁₀C of the total weight of aromatic hydrocarbons less than 5 weight %₁₀Aromatic hydrocarbons includes durene, or A combination thereof.

16. the conversion effluent of any one of -13 preparations according to claim 1.