CN1173486A

CN1173486A - Preparation of methylamines using shape selective chabazites

Info

Publication number: CN1173486A
Application number: CN97113436A
Authority: CN
Inventors: F·C·威廉; T·R·加夫尼; G·E·帕里斯; B·A·奥夫丹姆布林克
Original assignee: Air Products and Chemicals Inc
Current assignee: Air Products and Chemicals Inc
Priority date: 1993-07-01
Filing date: 1997-05-22
Publication date: 1998-02-18
Anticipated expiration: 2014-07-01
Also published as: CN1122017C; JPH07145113A; JP2856383B2; CA2126834A1; CA2126834C; CN1040531C; CN1102827A

Abstract

The present invention relates to a process for reforming of a methylamine containing feedstock in the presence of a catalyst. The key to achieving this low TMA selectivity at high conversion resides in the use of a microporous zeolite, preferably composed chabazite catalyst, which has a geometric selectivity index (GSI) less about 3, a shape selectivity index (SSI) greater than about 5 and a sorption capacity for 1-PrOH of at least 0.5 mmol/g. The positive ions of composed chabazite catalyst are mainly selected from the alkali ions of H, Li, Na, K, Rb and Cs.

Description

Utilize the method for shape selective chabazites Preparation of Catalyst methylamine class mixture

The application is that submission day is the part continuation application of the common transfer U. S. application 08/086497 on July 1st, 1993, and its subject matter is incorporated by reference.

The present invention relates to a kind of use composition as catalyzer,, produce the method for the methylamine class mixture that comprises single methylamine, dimethylamine and Trimethylamine 99 by the catalytic reforming of the material that contains single methylamine.

Prepare the methylamine class by methyl alcohol and ammonia, the reaction that comprises the mixture of single methylamine, dimethylamine and Trimethylamine 99 is the reaction that people know, this reaction product is a kind of equilibrium mixture, it is by single methylamine (MMA) of about 35 weight % of reaction product, the Trimethylamine 99 (TMA) of the dimethylamine of 27 weight % (DMA) and 30 weight % is formed, and these reaction product are be 350 ℃, 1 barometric point and ammonia with the ratio (N/R) of methyl alcohol in temperature is to generate under 3.5 the condition.People have use up very big effort develops some novel procesies, and these technologies will change the expection product that is generated by methyl alcohol and ammonia react.The technology variable factor that can influence (though limited) expection product comprises time-space relationship, ammonia mol ratio and the temperature to methyl alcohol.The change of expection product mainly be the catalyzer selected by shape for example zeolite reach.

Following representative patents has been described the various technical process that is prepared the methylamine reaction product by methyl alcohol and ammonia react, and prepared reaction product has MMA, DMA and the TMA of non-equilibrium content.

US 4,485,261 disclose a kind of preparation technology of methylamine reaction product, be rich in DMA in this methylamine reaction product, and only containing a spot of TMA, this technology comprises that the mixture with methylamine and ammonia is added in a kind of porosu solid an acidic catalyst that comprises silicon-dioxide, aluminum oxide, Y type and X type zeolites, forms the primary reaction product thus, then ammonia and a kind of aperture be 3～8A the crystalline silicon aluminate in the presence of, make at least a portion reaction product generation catalytic reforming reaction.Below list the catalyzer that has 3～8A aperture in a large number, these catalyzer comprise clinoptilolite, erionite, mordenite, chabazite and various synthetic zeolite.US 4,205, and 012 discloses the technology that amine is produced in a kind of reaction by alkanol and ammonia, for example, in the presence of the FU-1 zeolite, make methyl alcohol and ammonia react prepare methylamine, sodium cations all basically in this FU-1 zeolite are replaced by divalent cation and three rank positively charged ions.

US 4,602, and 112 disclose a kind ofly in the presence of acid H-ZSM-5 zeolite catalyst, make methyl alcohol or dme and ammonia react, and highly selective prepares the technology of DMA.

US 3,384, and 667 disclose a kind ofly in the presence of the dehydration crystalline silicon aluminate catalyst of natural formation, make ammonia carry out the technology of alkylated reaction, and the aperture of this catalyzer makes it can only adsorb primary amine and secondary amine product, and can not adsorb the tertiary amine product.The example of natural zeolite comprises: iron alkali zeolite, chabazite, erionite and mordenite.

US 4,737,592 disclose a kind of in the presence of acidic zeolite catalyst, make methyl alcohol and/or dme and ammonia react prepare the technology of the reaction product that is rich in DMA, this acidic zeolite catalyst is selected from natural chabazite, H-exchange chabazite and M-exchange chabazite, and wherein every kind of chabazite all has and is higher than 3 geometry selectivity index (GSI).The alkalimetal ion that is suitable for exchanging comprises sodium, potassium, rubidium and caesium.

US 4,458, and 092, US 4,398,041 and US 4,434,300 disclose the technology of utilizing zeolite catalyst to react to prepare methylamine.US 4,458, and 092 discloses the use through the Y-zeolite of the peracidity dehydrated aluminosilicate catalyzer of rare earth exchanged or hydrogen metal ion exchanged.US 4,434, and 300 disclose the technology of utilizing macroporosity H-chabazite-erionite to prepare amine as preferred amination catalysis.At Condar (Anaconda) chabazite-erionite is used as a kind of special efficacy catalyzer, and this catalyst system can make methyl alcohol reach high conversion, and the generation of TMA seldom.

US 4,254,061 and US 4,313,003 disclose and be rich in MMA (US 4,254,061) and be rich in the methylamine preparation method of DMA (US 4,313,003).US 4,254,061 discloses in the presence of mordenite, erionite, clinoptilolite etc., make methyl alcohol and ammonia react prepare the method for MMA, and US 4,313,003 discloses at US 4, under the existence of the catalyzer of mentioning in 254,061, prepare the reaction of the reaction product that is rich in DMA with MMA and ammonia react.

US 4,082, and 805 disclose in the presence of the crystalline silicon aluminate with ZSM-5, ZSM-11 or ZSM-21 structure, with C ₁～C ₅Alcohol or ether and the ammonia react method for preparing amine.

The present invention relates to a kind of improvement technology that is used to prepare methylamine reaction product with the non-equilibrium content of TMA.Generate one of many basic craft course of methylamine reaction product with methyl alcohol/dme excellent conversion and low Trimethylamine 99 content, be included under the existence of zeolite catalyst, make methyl alcohol/dme and ammonia, single methylamine, dimethylamine and Trimethylamine 99 reaction.On the other hand, producing the other method that is rich in the methylamine reaction product is with catalyzer the material that contains single methylamine to be reformed.Produce a part of improvements of primary process of the reaction product of the low and methyl alcohol/dimethyl ether conversion rate excellence of Trimethylamine 99 content, be to utilize a kind of zeolite catalyst, this zeolite catalyst mainly comprises a kind of zeolite, chabazite preferably, this zeolite has approximately the shape selective index (SSI) greater than 5, the 1-propyl alcohol adsorptive value that is lower than 3 GSI and is higher than 0.5mmol/g.Typically, shape-selective zeolite or synthetic chabazite and alkalimetal ion such as sodium, potassium, rubidium and caesium exchange.The second section of this primary process improves and is that the material that will contain single methylamine passes through this catalyzer, thereby this single methylamine is restructured as the expection product that is rich in dimethylamine.

Utilization has the zeolite and the synthetic chabazite of aforesaid SSI exponential sum propyl alcohol adsorptive value, several significant benefits below desirable the getting:

Can prepare and a kind ofly be rich in single methylamine and dimethylamine, and the very low reaction of Trimethylamine 99 content

Product;

Can prepare methylamine by the methyl alcohol amination reaction of speed of reaction excellence;

Can prepare the reaction product that comprises multiple methylamine by excellent methanol conversion;

The content distribution unbalance response that can prepare single methylamine, dimethylamine and Trimethylamine 99 is produced

Thing;

Can in the sufficiently long time, carry out methyl alcohol amination operation and the catalyzer mistake does not take place

Live;

Can the non-stop run a very long time; Light and the material that will contain single methylamine is by catalysis

Agent recirculation, and obtain a kind of nonequilibrium expection product.

Fig. 1 is the SSI of a large amount of chabazite catalyzer of expression (comprise baked and not the catalyzer of roasting) and the correlationship figure between the GSI.

Fig. 2 is the shape selective index of expression chabazite baked and not roasting two kinds of catalyzer and to the graph of a relation between the selectivity of TMA.

Fig. 3 is for geometry selectivity index (GSI) of the synthetic chabazite catalyzer of comparing with the natural chabazite catalyzer and to the optionally graph of a relation of TMA.

One of Basic Ways of preparation alkylamine is the aminating reaction of alkanol and alkyl ether. Produce The approach of methylamine generally includes methyl alcohol (MeOH) and/or dimethyl ether (DME) and ammonia, MMA (MMA), dimethylamine (DMA) or trimethylamine (TMA) carry out under the condition of amination being enough to carry out Reaction, raw materials used available supply and the desired product of expecting of depending on. Be typically, Nitrogen/carbon (N/R) mol ratio in about 0.2～10 scope, preferably in 1～5 scope, Reaction temperature about 225 ℃～450 ℃ preferably at 250～375 ℃) scope in. Reaction pressure Power can change, but typical scope is 50～1000psig, preferred 150～500psig. Total charging air speed is about 200～8000 hours^-1, be preferably 500～5000 hours^-1 Art Language " air speed " or GHSV are defined as the charging speed of gas hourly under the standard temperature and pressure (STP) Rate is (with cm³Meter) to the volume of catalyst bed body (with cm³Meter) ratio.

Resulting by methyl alcohol and/or DME to the conversion ratio of methylamine usually about 50%～In 100% the scope (take the mole of methyl alcohol as benchmark), and to the overall selectivity height of methylamine In 95% % by weight, and TMA content is lower, is 20 % by weight or lower, is usually less than 15 % by weight. Be typically, the percentage by weight of MMA in product is 36～50 In the scope of % by weight, and the percentage of DMA in product is in 25～60 % by weight In the scope.

The material that another kind is suitable for this method contains MMA. This MMA is through this catalyst Be restructured as the expection product that is rich in dimethylamine. In this material, can also exist or not exist ammonia and Other component is such as trimethylamine. But, when adding trimethylamine in the material, can't see expection Product significant benefit is arranged.

Obtain high conversion and fabulous reaction rate and the low Amination Technique of TMA product content Key problem in technology, be to utilize a kind of microporosity catalyst system, the geometry of this system is selective Index (GSI) is lower than 3, and it is about 5 that shape selective index (SSI) is higher than, and every gram catalyst is inhaled Attached 1-PrOH at least about 0.5mmol (1-PrOH of 3 % by weight). Preferred catalyst system A kind ofly to be about the catalyst that 7～25 synthetic chabasie forms by SSI. Term " shape choosing Select sex index " (SSI) define with following formula:

SSI=is at 20 ℃ and relative pressure P/P₀Be under 0.5 the condition, by catalyst 25

The amount of the 1-PrOH of absorption is divided by the amount that is adsorbed 2-PrOH in the hours.

Absorption represents that with % by weight namely, per 100 restrain the sorption that zeolite catalysts adsorb

The grams of thing.

In the presence of the chabasie catalyst system, carry out the many existing technology mistake of methanol amination Journey is that the chabasie with natural formation carries out. Successfully catalytic amine reaction of natural chabazite Key is US 4,737, pointed geometry selectivity index (GSI) in 592, and its GSI value must Must be greater than about 3. How much selectivity index define with following formula:

GSI=is at 25 ℃ and relative pressure P/P₀Be under 0.1 to 0.5 the condition, measured

Be exposed to the methyl alcohol (MeOH) of clean absorption in 20 hours in the sorbate steam by zeolite

Amount is divided by 1-PrOH (n-PrOH) amount of clean absorption. Absorption represents with % by weight,

Be the adsorbed sorbate gram numbers of per 100 gram zeolites.

Have been found that GSI can not be used for entirely judging this catalyzer selectivity or active aspect validity.Particularly synthetic chabazite catalyzer selectivity and active aspect do not follow this parameter.Also find simultaneously, adsorb relevant parameter with the 1-propyl alcohol, can predict more accurately as the zeolite of the catalyzer particularly activity and the shape selective of chabazite by using a parameter that is referred to as shape selective index (SSI) and another.SSI can be used to evaluate the size and the shape in open pore or hole, and GSI then utilizes the molecule completion method to assess the size in hole.Along with the increase of SSI value, the size of microvoid structure and/or shape at preferentially adsorbed 1-PrOH to a greater extent, and are repelled 2-PrOH.Since use the branched-chain alcoho 2-PrOH different with straight chain alcohol, so SSI more emphasizes the size and the shape of catalyzer perforate, rather than the size in hole and shape, though it is all taken two kinds of effects into account.GSI uses straight chain alcohol in its mensuration, therefore, it is more useful how being filled in the small hole at the appraisal molecule, but it does not indicate the ability that catalyzer allows reactant or product to infiltrate from cage structure.If catalyzer is only occupying by positively charged ion or lattice parameter changes and to have any different aspect the hole size cause, then the correlationship between these two notions is clearly.

Require catalyzer to have minimum adsorptive value that a kind of tolerance that catalyzer under the temperature of technology and air speed is obtained the ability of high methyl alcohol speed of reaction is provided to the 1-propyl alcohol, this high methyl alcohol speed of reaction for example is to be higher than 50%, the conversion usually above 75%.The catalyzer that the propyl alcohol adsorptive value is low though it has high SSI value or high GSI value, may can provide shape selective, but methyl alcohol/dimethanol transformation efficiency that it is also gone on business demonstration usually.

Metallic cation in zeolite structured to the SSI value of catalyzer and active the two all exert an influence.The adsorptive power of big metallic cation restriction zeolite framework, and reduce the ability that it adsorbs the 2-propyl alcohol.Positively charged ion in zeolite framework (for example H) may not be localized or not occupy enough spaces, the equilibrium distribution that this causes zeolite to have low SSI value and cause methylamine.Should select suitable positively charged ion,, and have enough acidity and keep its activity so that the SSI of zeolite or chabazite is in the preferred range.Operational representational positively charged ion comprises H, Li, Na, K, Rb, Cs, Mg, Ca, Ba, Al, Ga, Fe, Sr, La, Cu, Zn, Ni, B, Ce, Sn and Ru.Wherein, basic metal K and Na are preferred.

This class chabazite preparation methods is known, and does in receipts to have enumerated example among the US 4,925,460 of reference of the present invention.After preparation, preferably chabazite is heated at least 375 ℃ temperature, to carry out the roasting of catalyst system.Though unfired catalyst system and baked catalyst system may be used in the practice of carbinolamine metallization processes, but baked chabazite has higher methanol conversion speed than not baked chabazite system, and through the synthetic chabazite system of roasting the content of TMA is reduced.

As all shape selective catalyzer, catalyzer is given shape selective with " overload " ability.When this happens, the expection product just approaches equilibrium distribution.When katalysis by the hole network transitions of zeolite during to surface catalyst, shape selective has just diminished.Can cause the factor of methylamine product equilibrium distribution to have by the shape selective catalyzer many, and these factors comprise too high temperature, low air speed, and the catalyzer coking, or the like.Particularly, temperature of reaction is to expect that product is a kind of main method of equilibrium distribution by shape selective distribution transfer.The following example is used for explaining various embodiments of the present invention, and makes comparisons with prior art.Unless stated otherwise, all per-cents are all represented weight percent.

Embodiment 1

The preparation of synthetic potassium chabazite

Press Coe and Gaffney at United States Patent (USP) 4,925, the conventional steps in 460 has prepared the sample of potassium chabazite.More particularly, ammonium-y-type zeolite LZY62 extrudates that 48 grams are obtained by UOP 500 ℃ of following roastings 2 hours, cool off then and make it moistening.To join and be impregnated into a kind of colloid silica (14%SiO subsequently by 189 grams through moistening extrudate ₂) and the aqueous premix of the 1M KOH of 672ml in.In the Nalgene bottle that separates, carry out 9 times this dipping simultaneously.This mixture kept 96 hours under 95～100 ℃ temperature.Solid is reclaimed and use deionized water wash, reach till 7 up to the pH value.Ultimate analysis has provided the following composition of representing with oxide weight %: 17.80%K ₂O, 0.02%Na ₂O, 24.30%Al ₂O ₃And 56.50%SiO ₂Si/Al is overall than being 1.97, the Si/Al in the skeleton structure compare with ²⁹Si MASNMR method is measured as 2.4.X-ray diffraction spectrum shows that product is specpure chabazite, does not have trace y-type zeolite pollutent.Should (K+Na) show have 80% Al to be present in the skeleton structure of zeolite approximately with the ratio of total Al content.

Embodiment 2

The preparation of the synthetic chabazite of ammonium exchange

The sample of the chabazite of ammonium exchange carries out ion-exchange with Partial K-chabazite sample of producing among the embodiment 1 and prepares.The K-chabazite of hydration is joined the NH of 30 weight % ₄NO ₃In the solution, its ratio is that 2ml solution restrains chabazite to 1, then is heated to 95～100 ℃, and keeps 2 hours under this temperature, then solid is reclaimed, and uses the deionized water thorough washing.This exchange and washing step repeat 5 times again.After 110 ℃ of following dryings, obtain the NH of 450 grams ₄-chabazite product.Remaining K constitutes about 11% ion-exchange capacity.

Embodiment 3

The preparation of the synthetic chabazite of 95% potassium exchange

The sample of potassium exchange chabazite is the part NH that makes among the embodiment 2 ₄-chabazite carries out ion-exchange and makes.At first with 30 gram exsiccant NH ₄-chabazite is wetting and at 95～100 ℃, in 2 hours, is added to the 1M KNO of 300ml ₃In the solution, then solid is reclaimed, and use deionized water wash.Should exchange and washing step repeats once again.The ultimate analysis of product has provided the following composition of representing with oxide weight %: 17.17%K ₂O,＜0.02%Na ₂O, 24.6%Al ₂O ₃, and 56.0%SiO ₂The K content of this sample constitutes about 94.5% ion-exchange capacity.

Embodiment 4

The preparation of the synthetic chabazite of 58% sodium exchange

The sample of sodium exchange chabazite is the part NH that makes among the embodiment 2 ₄-chabazite carries out ion-exchange and makes.At first with 50 gram exsiccant NH ₄Chabazite is wetting, at 95～100 ℃, in 2 hours, it is added to the 1MNaNO of 300ml ₃In the solution, reclaim solid then and use deionized water wash.Should exchange and washing step repeats 1 time again.The ultimate analysis of product has provided the following composition of representing with oxide weight %: 1.32%K ₂O, 7.63%Na ₂0,27.20%Al ₂O ₃, and 64.20%SiO ₂The Na of this sample and K content constitute about 57.5% and 6.5% ion-exchange capacity respectively.

Embodiment 5

The preparation of the synthetic chabazite of＞99% sodium exchange

The sample of sodium exchange chabazite is the part NH that makes among the embodiment 2 ₄-chabazite carries out ion-exchange and makes.At first, with the 30 dry NH that restrain ₄-chabazite is wetting, at 95～100 ℃, is added to the 1M NaNO of 1000ml in 2 hours ₃In the solution, reclaim solid then, and with passing through the distillatory deionized water wash.Should exchange and washing step repeats 5 times again.The ultimate analysis of product has provided the following composition of representing with oxide weight %: 0.05%K ₂O, 12.66%Na ₂O, 25.80%Al ₂O ₃, and 61.20%SiO ₂The Na of this sample and K content constitute ion-exchange capacity approximately＞99% and 0.5% respectively.

Embodiment 6

The preparation of the synthetic chabazite of 66% sodium exchange

The preparation of sodium exchange chabazite comprises following three steps.These steps are:

A. potassium chabazite sample is by the common step preparation of embodiment 1.At first restrain LZY 64 extrudates 500 ℃ of following roastings 2 hours, then cooling and it is wetting with 150.Then, moistening extrudate is joined and impregnated in a kind of NalCO by 630 grams ^TM2326 colloid silica (14%SiO ₂) and the aqueous premix of 2240ml 1M KOH in.In the Nalgene bottle that separates, carry out 3 such dip operation simultaneously.This mixture kept 96 hours down at 95～100 ℃.Solid is reclaimed, merge, and reach till 7 until the pH value with deionized water wash, dry down at 110 ℃ then.N+Na shows have 84% Al to be present in the skeleton structure of zeolite with the ratio of total Al content.

B. the sample of ammonium exchange chabazite prepares by synthetic Partial K chabazite sample in the steps A is carried out ion-exchange.At first, the exsiccant K-chabazite of 50 grams is moistening, at 95～100 ℃ of NH that in 2 hours, join 120ml 30 weight % ₄NO ₃In the solution, then, reclaim solid, and use the deionized water thorough washing.Should exchange and washing step repeats 5 times again.

C. sodium exchange chabazite is the NH that makes among the step B ₄The chabazite sample carries out ion-exchange and makes.With all hydration NH ₄-chabazite joined 300ml 1M NaNO at 95～100 ℃ in 2 hours ₃In the solution, then solid is reclaimed, and use deionized water wash.Should exchange and washing step repeats 1 time again.The ultimate analysis of product has provided the following composition of representing with oxide weight %: 0.28%K ₂O, 8.46%Na ₂O, 25.20%Al ₂O ₃, and 66.10%SiO ₂The Na of this sample and K content constitute about 66% and 1.4% ion-exchange capacity respectively.

Embodiment 7

The preparation of the synthetic chabazite of potassium exchange

Potassium chabazite sample is that the impregnation steps by embodiment 6 prepares, the LZY 64 of different have been to use different lot numbers.

Embodiment 8

The preparation of the synthetic chabazite of 80% sodium exchange

Sodium exchange chabazite sample carries out ion-exchange with the Partial K-chabazite sample that makes among the embodiment 7 and makes.At first, 50 gram exsiccant K-chabazites are moistening, at 95～100 ℃ of 1MNaNO that in 2 hours, join 1665ml ₃In the solution, then solid is reclaimed, and use deionized water wash.Should exchange and washing step repeats 1 time again.The ultimate analysis of product has provided the following composition of representing with oxide weight %: 3.76%K ₂O, 10.02%Na ₂O, 24.4%Al ₂O ₃, and 62.00%SiO ₂The Na of this sample and K content constitute about 80% and 20% ion-exchange capacity respectively.

Embodiment 9

The preparation of the synthetic chabazite of 99% sodium exchange

The sample of sodium exchange chabazite is to carry out ion-exchange by the Partial K-chabazite that will make among the embodiment 7 to make.At first, with 50 the gram dry K-chabazites wetting, under 95～100 ℃ in 2 hours, join the 1M NaNO of 1665ml ₃In the solution, reclaim solid then, and use deionized water wash.Should exchange and washing step repeats 5 times again.The ultimate analysis of product has provided the following composition of representing with oxide weight %: 0.23%K ₂O, 12.37%Na ₂O, 24.50%Al ₂O ₃, and 62.80%SiO ₂The Na of this sample and K content constitute about 99% and 1% ion-exchange capacity respectively.

Embodiment 10

The roasting of the synthetic chabazite of ammonium exchange

The ammonium of preparation among the embodiment 2 is exchanged sample roasting in 350 ℃ air of chabazite.The desciccate that embodiment 2 makes is put into 110 ℃ muffle furnace, be warming up to 350 ℃ with about 5 ℃/minute heat-up rate then, and kept 2 hours in this temperature.The ultimate analysis of product of roasting has provided the following composition of representing with oxide weight %: 2.46%K ₂O, 0.02%Na ₂O, 29.20%Al ₂O ₃, and 6830%SiO ₂

Embodiment 11～15

The roasting of the synthetic chabazite of cationic exchange

With embodiment 4,5, the chabazite sample of 6,8 and 9 cationic exchange that make is by the common method for making that provides among the embodiment 10, individually 450 ℃ of following roastings.Treatment process is as shown in table 1.

Table 1

Embodiment raw material precursor calcination atmosphere embodiment 11 embodiment 4 LZY62 air embodiment 12 embodiment 5 LZY62 air embodiment 13 embodiment 6 LZY64 air embodiment 14 embodiment 8 LZY64 air embodiment 15 embodiment 9 LZY64 100% water vapor

Embodiment 16～21

Geometry selectivity and shape selective index

Measure the GSI and the SSI of several catalyzer according to adsorption step described above.More particularly, GSI determines like this: when catalyzer is exposed in the sorbate steam 20～24 hours under 20 ℃, measure the absorption that methyl alcohol and 1-PrOH fasten at catalyst body.The mensuration of how much selectivity index (GSI) is undertaken by the usual method in the U.S. Pat 4,737,592.In measuring shape selective index (SSI) process, each catalyst sample all will carry out degasification, and the speed with 1 ℃ of per minute is warming up to 400 ℃ on the spot, and keeps 10～12 hours under the vacuum of 0.1 milli torr.Then each catalyst sample is cooled to 20 ℃.And at relative pressure (P/P ₀) be under 0.5 the condition, make it be exposed in the corresponding steam about 24 hours.The adsorption temp of methyl alcohol, 1-PrOH and 2-PrOH is 20 ℃.The absorption of every kind of catalyst system is 2-PrOH, 1-PrOH and methyl alcohol in proper order.After being exposed to every kind of sorbate steam, under 400 ℃ and vacuum, make and examined the catalyzer degasification and spend the night, and claim the weight of catalyst sample, determine whether that with this all sorbate steams all are removed.If a part of sorbate steam is retained, and do not reach the original dry weight of catalyst system, then examined catalyzer degasification once more.Calculate corresponding index.

Following table 2 has been listed natural catalyst system and their the corresponding GSI value and the SSI value of synthetic catalyst system.Natural chabazite only is used for illustrative purposes.With regard to their true nature, these mineral are not only different between each natural mineral deposit, and difference is also arranged in same mineral deposit.

Table 2 embodiment catalyzer MEOH N-PROH I-PROH GSI SSI

(mmol/g) (mmol/g) (mmol/g) embodiment 1 100%K chabasie 5.19 2.29 0.10 1.21 22.90 embodiment 3 95%K chabasies 5.10 1.53 0.10 1.78 15.30 embodiment 4 58%Na chabasies 5.03 2.33 0.33 1.15 7.06 embodiment 5 99%Na chabasies 6.24 3.03 0.14 1.10 21.64 embodiment 10 11%K chabasies 4.49 1.48 0.16 1.62 9.25 embodiment 11 58%Na chabasies 5.05 2.33 0.25 1.16 9.32 embodiment 12 99%Na chabasies 5.21 1.81 0.12 1.53 15.08 embodiment 13 66%Na chabasies 6.15 2.95 0.42 1.11 7.02 embodiment 15 99%Na chabasies 1.66 0.15 0.10 5.90 1.50 embodiment 16 DURKEE^*5.94 0.94 0.23 3.37 4.09 embodiment, 17 NOVA SCOTIA ^*7.14 1.20 0.05 3.19 23.90 embodiment, 18 CHRISTMAS ^*5.06 2.39 0.51 1.13 4.69 embodiment, 19 BOWIE ^*6.36 2.97 0.76 1.14 3.91 embodiment, 20 BUCKHORN ^*4.61 1.36 0.17 1.81 8.00 embodiment, 21 LAZ62 5.90 3.11 2.87 1.01 1.08 ^*These are zeolites of natural formation.

Embodiment 22

Methyl alcohol amination reaction: chabazite catalyzer

Utilize different catalyst systems, make methyl alcohol and ammonia react, carry out several methyl alcohol amination reactions.Table 3 has been listed the explanation of catalyzer, its source and reaction conditions, and table 4 has been listed the result of each reaction.

Table 3

Catalyzer and reaction conditions

Catalyst type mol ratio GHSV temperature, pressure sequence number embodiment catalyst n/R (l/hr) (℃) (PSIG) 1 EX1 100%Kchab 3.5 1,000 350 250

Roasting 375 2502 EX3 95%Kchab 3.5 1,000 350 250 not

Roasting 3.5 500 350 250

2.3 1000 350 250

2.3 500 350 2503 EX4 58％NaChab 3.5 1000 350 250

Roasting 3.5 500 350 2504 EX5 99%NaChab 3.5 1,000 350 250 not

Roasting 3.5 500 350 2505 EX11 58%NaChab 3.5 1,000 350 250 not

Roasting 6 EX12 99%NaChab 3.5 1,000 350 250

Roasting 7 EX13 66%NaChab 3.5 1,000 350 250

Roasting 8 EX15 99%NaChab 3.5 1,000 350 250

Roasting

Table 4

Reaction conditions and result

MeOH % sequence number N/R GHSV (℃) (PSIG) GSI SSI transformation efficiency % TMA selectivity 1 3.5 1,000 350 250 1.21 22.90 51 6

3.5 1000 375 250 62 5 2 3.5 1000 350 250 1.78 15.30 65 7

3.5 500 350 250 86 6

2.3 1000 350 250 62 5

2.3 500 350 250 81 6 3 3.5 1000 350 250 1.15 7.06 94 33

3.5 500 350 250 96 20 4 3.5 1000 350 250 1.10 21.64 76 4

3.5 500 350 250 90 4 5 3.5 1000 350 250 1.16 9.32 98 15 6 3.5 1000 350 250 1.53 15.08 73 4 7 3.5 1000 350 250 1.11 7.02 99 13 8 3.5 1000 350 250 5.90 1.50 34 1

In contrast, Fig. 3 geometry selectivity index (GSI) and TMA of showing synthetic chabazite catalyzer optionally concerns.As can be seen from Figure, utilize low GSI value can reach the excellent selectivity and the activity of producing about methylamine.Therefore, in the catalyzer fundamental property, SSI is a more useful parameter.

Sum up:

Experiment 1 and 4 demonstrates, and the cation type in the calcined catalyst does not optionally influence to methanol conversion with to TMA.In the experiment 4 and 6＞99% cation exchange capacity shows that the Na cation type under high SSI value gives higher transformation efficiency than K cation type catalyzer (testing 2).The SSI value of Na exchange catalysts and K exchange catalysts is respectively about 22 and 23, and the TMA selectivity ratios equilibrium value 35 weight % that give are much lower.The GSI value that catalyzer provides is lower than 3.Have so similar SSI value, the difference of transformation efficiency has reflected cationic type, rather than the hole diffusional resistance.

Experiment

1 and 2 demonstrates, by with NH ₄ ⁺Partly exchange or K ⁺Even GSI is lower than 3, the K cation type also can improve conversion of methanol.Keep these not the SSI value of calcined catalyst be higher than about 7, selectivity to TMA is still very low, by to testing the 3 and 4 this effects that more also can find out the Na cationic catalyst, transformation efficiency is increased to 94% by 76% in experiment 3 and 4, and TMA still is lower than 35 weight %.

Experiment 7 and 8 shows, for the 99%Na chabazite, concerning methylamine is synthetic, does not wish that the SSI value is lower than 3.Experiment 8 has utilized a kind of 1-PrOH adsorptive power to be lower than the catalyzer of 0.5mmol/g.In this case, cause the low reason of SSI value to be that it repels 1-PrOH and 2-PrOH significantly, and on the other hand, be about 6 GSI value and show that methyl alcohol is still and be easy to into.According to prior art, because this catalyzer only is 1 weight % to the selectivity of TMA, this shows that its activity still arranged by the zeolite internal surface, so it is exactly a kind of acceptable catalyzer.Yet its transformation efficiency (34%) is unacceptable, that is to say, under 350 ℃, its transformation efficiency is lower than 50%.

Experiment

3 and 5 and 4 and 6 demonstrates the effect of

roasting.In experiment

3 and 5, not roasting Na chabazite for 58% and roasting Na chabazite, the GSI value remains below 3, but SSI is increased to 9 because of roasting by 7, and this causes the selectivity of TMA is reduced to 15 weight % by 33 weight %.And simultaneously, transformation efficiency is increased to 98% by 94%.It is as lively as a cricket that experiment 3 demonstrates that the catalyzer of not roasting compares with the type of roasting, but with regard to TMA, it is a rather non-selective.Under very high SSI value, for example＞25, people expect that the hole diffusional resistance can limit transformation efficiency and to the selectivity of TMA, katalysis at this moment will be only limited to surface catalysis, and product will approach equilibrium distribution.Have at catalyzer and to be higher than about 99% exchangeable cation (as Na), and the SSI value is respectively in 22 and 15 the experiment 4 and 6, only have slight influence or not influence fully to transformation efficiency or to the TMA selectivity 450 ℃ of following roastings.

The shadow that experiment 5,6 and 7 is illustrated in cationic exchange in a series of calcined catalyst to, these catalyzer are lower than 3 with the GSI value, and the SSI value is in 7～15 scope.The Na cationic exchange is reduced to 66% by 99%, makes transformation efficiency be increased to 99%, and the selectivity of TMA is increased to 13 weight % by 4 weight % by 73%.As Na exchange further is reduced to 58% by 66%, then under above-mentioned processing condition, can not show the benefit that has on the transformation efficiency, be increased to 15 weight % and the TMA selectivity added as by 13 weight %.

Fig. 1～3rd drawn according to above-mentioned every experiment institute data that obtain and to be formed, and its purpose is with the diagrammatic form assessment as predicting that amination expects the SSI value of means of product.Fig. 1 comprises the figure of marking and drawing with table 3 and table 4 data.It show concerning a large amount of chabazite catalyzer, do not exist between the SSI and GSI relevant.Fig. 2 is for SSI and TMA optionally schemed, and the SSI value that it demonstrates baked and unfired chabazite catalyzer is for to TMA adverse effect optionally.Find out that by Fig. 2 when the SSI value increased, the degree that the size of microvoid structure and/or shape are preferentially repelled 2-PrOH was much higher than 1-PrOH's.Therefore, have and be about 7 or the not calcined catalyst of higher SSI value, can give the TMA selectivity is 35% or lower.Have be about 3 or the calcined catalyst of higher SSI value can produce analog result.

Embodiment 23

Methyl alcohol amination reaction: comparison process research and alkaline purification research

Utilize various different catalysts systems, make methyl alcohol and ammonia react and carried out a series of methyl alcohol amination simultaneous test.

The chabazite of alkaline purification is like this preparation: 20 gram K-chabazite samples are put into the KOH solution of 200ml0.5M, do not stir down and be heated to 100 ℃, be 2 hours heat-up time.Solution is drained solid about 5 minutes with deionized water wash from solid.Repeat this treatment step, difference is that mixture was kept 16 hours down at 100 ℃.With distilled water wash and in addition after the drying, sample is analyzed, show that sample contains 21.2% Al ₂O ₃, 57.7%SiO ₂And 17.37%K ₂O.

Then, sample is put into a water-filled closed container, on permeable gas testing surface ware, keep 16 hours so that it is moistening.Spend 1 hour at 100 ℃ and use 30%NH ₄Cl (10ml/g) is with sample preparation 3 times.After each the processing, with samples with water washing 10 minutes.Will be dry under 110 ℃ through the sample of exchange, and 450 ℃ of following roastings 2 hours.

Table 5 is listed catalyst type, the result of its source and each reaction.Unless stated otherwise, all experiments all are at 350 ℃, GHSV=1000 hour ^-1, N/R=3.5, pressure=250psig condition under carry out.

Table 5 sequence number embodiment catalyzer source GSI SSI % transformation efficiency %MMA % DMA %TMA 1 non-crystalline state Al ₂O ₃/ SiO ₂AKZO N/A N/A 77 39 23 38 2 natural H type chabazite AW500 1.03 1.81 97 36 25 39 3 synthetic H type chabazite LZY64 N/A N/A 98 37 26 37 4 synthetic alkalis are handled LZY64 2.21 12.5 96.7 44.1 48.7 7.2 H ⁺Chabazite ^*300 ℃ of 5 synthetic alkali handled LZY62 2.21 12.5 94.2 23.1 51.5 25.4 H ⁺Chabazite ^*350 ℃

The

experiment

1 and 2 of table 5 illustrates the comparative data of the H type natural chabazite of amorphous silicon di-oxide-aluminium oxide catalyst and AW500.The 1-PrOH adsorptive value of the H type of natural chabazite is up to 2.39mmol/g.Therefore, these data show, though its GSI value is less than 3, the SSI value reaches than amorphous catalyst (it is more active) or the higher transformation efficiency of some synthetic chabazite less than the H type of 5 natural chabazite, its similar to the amorphous catalyst of TMA selectivity and experiment 1.

The experiment 2 of table 5 and 3 is a comparing embodiment, and it demonstrates the H type of natural chabazite and two kinds of catalyzer of H type of synthetic chabazite all obtain close high conversion and the distribution of non-selected methylamine.Do not introduce shape selective.Adopted shape to select H type alkaline purification catalyzer and test 4 and 5.This catalyzer has the H that is arranged in skeleton structure ⁺Ion is so that it can improve reaction and shape selective.

The SSI value is that the synthetic chabazite of 5 to 25 roasting can reach the highest methanol conversion, and the TMA selectivity that is actually lowest percentage.As a comparison, the GSI value is higher than 3 chabazite, though also effective, catalytic activity is not enough.

The SSI value is particularly the importance when its numerical value surpasses 5, illustrated that the SSI value is in methyl alcohol/dimethyl ether conversion rate with to the importance aspect the TMA selectivity percentage ratio.For example, be partial to the synthetic chabazite of the low end of its scope for a kind of its SSI value, the synthetic chabazite of roasting not for example, it significantly improves TMA selectivity percentage ratio, and catalyzer keeps high reactivity.

Embodiment 24

The reformation of single methylamine material

Repeat the step of example 23, just replace methyl alcohol as material with containing the monoamine material.A kind of is the material that contains 30% single methylamine in ammonia, and another kind is pure single methylamine.Catalyst system therefor is the chabazite of hydrogen/potassium exchange in the reaction, the chabazite of alkaline purification in the example 23.Table 6 has been listed reaction conditions and result.

Table 6

MMA reforms on the chabazite catalyzer, reaction conditions and result

NH ₃/ MeOH 300%MMA ^*The pure MMA transformation efficiency of pure MMA % 94.9 91.5

MMA 26.4 28.8 23.9 19.6

DMA 69 66.2 72.4 72

TMA 4.6 5 3.7 8.4

Temperature 300 300 300 300

N/R 1 1 1 1

GHSV 1,000 1,000 1000 500* materials are for containing 30%MMA in ammonia

The above results shows, uses the chabazite catalyzer can obtain single methylamine and is converted into extremely excellent transformation efficiency of dimethylamine and selectivity.The productive rate of TMA is extremely low.The result shows that adding ammonia in single methylamine material can not make transformation efficiency that great reduction is arranged.

Claims

One kind in the presence of catalyzer, catalytic reforming by the material that contains single methylamine, production comprises the method for the methylamine class mixture of single methylamine, dimethylamine and Trimethylamine 99, it is characterized in that being lower than 3 in how much selectivity index, shape selective counts 5-25, the absorption of 1-PrOH is at least about 0.5mmol/g and the micropore catalyzer is made up of synthetic chabazite is basically reformed under existing, and wherein the positively charged ion that synthesizes in the chabazite mainly is the alkalimetal ion that is selected from H, Li, Na, K, Rb and Cs.
2. the micropore catalyzer that the process of claim 1 wherein is made up of the synthetic chabazite catalyzer of roasting basically.
3. the method for claim 2, reaction wherein are to be that 250～375 ℃ of temperature and N/R carry out under than 0.2～10 condition in temperature range.
4. the method for claim 3, reaction wherein is to carry out under the pressure of 50～1000psig.
5. the method for claim 4, reaction wherein is at 200～8000 hours ^-1GHSV under carry out.
6. the method for claim 5, reaction wherein are to carry out under N/R is 1～5 condition.