CN1057451A - A kind of preparation method of ether - Google Patents

Abstract

The present invention relates to a kind of zeolites as catalysts of using, generate the preparation process of mixture of ether or ether by alkene and alcohol reaction.

Description

A kind of preparation method of ether

The present invention relates to prepare a kind of processing method of ether with the catalyzed reaction of a kind of alkene and alcohol.

Zeolitic material no matter be natural or synthetic, has all shown the catalysis characteristics that has for various organic conversion reaction.Certain zeolitic material is to have as by the determined certain crystalline structure of X-ray diffraction, and is orderly, the porous crystalline aluminosilicate.Wherein, have a large amount of less cavitys, these cavitys may be with littler groove or micropores and are interconnected.These cavitys are the same with micropore size in specific zeolitic material.Because the size of these micropores has characteristic like this, promptly when the branch period of the day from 11 p.m. to 1 a.m that will repel large-size, receivability absorbs the molecule of certain size, these materials thereby be called as " molecular sieve ", and be used to the whole bag of tricks to bring into play the advantage of these characteristics.Such molecular sieve is no matter natural or synthetic comprises the variation range of the crystalline silicate of a very wide cation.These silicate can be described to a SiO ₄With the oxide compound of periodictable III A family element, as, AlO ₄The rigid three-dimensional reticulated structure, wherein, tetrahedral structure and Sauerstoffatom are made the covalent cross-linking bonding.Herein, total III A family element is 1: 2 as the ratio of aluminium and Siliciumatom and Sauerstoffatom.The tetrahedral electricity price that contains III A family's element such as aluminium is able to balance by comprise a positively charged ion in this crystal, as the positively charged ion of a basic metal or an alkaline-earth metal.This balance can be expressed, wherein, III A family element such as aluminium, with each positively charged ion, as Ca/2, Sr/2, Na, the quantity ratios of K or Li is equal to.One type positively charged ion can be fully, also can be partly in a common mode by another type, the positively charged ion that is used for ion exchange technique is replaced.With this cationic exchange method, just may select suitable positively charged ion for use and change the silicate characteristic of gained.

The existing processes technology has produced large quantities of synthetic zeolites.These many zeolites are named with letter or other appropriate flags, for example as: zeolite Z(United States Patent (USP) 2,882, No. 243), X zeolite (United States Patent (USP) 2,882, No. 244), zeolite Y (United States Patent (USP) 3,130, No. 607), zeolite ZK-5(United States Patent (USP) 3,247, No. 195), zeolite ZK-4(United States Patent (USP) 3,314, No. 752), zeolite Z SM-5(United States Patent (USP) 3,702, No. 886), zeolite Z SM-11(United States Patent (USP) 3,709, No. 979), zeolite Z SM-12(United States Patent (USP) 3,832, No. 449), zeolite Z SM-20(United States Patent (USP) 3,972, No. 983), zeolite Z SM-35(United States Patent (USP) 4,016, No. 245), with No. 4,076,842, zeolite Z SM-25(United States Patent (USP)).

The SiO of given zeolite ₂/ Al ₂O ₃Ratio is often to change.For example, X zeolite can be used from 2 to 3 SiO ₂/ Al ₂O ₃Ratio is synthesized, and zeolite Y then is from 3 to 6.In some zeolites, SiO ₂/ Al ₂O ₃The upper limit of ratio is unrestricted.Z SM-5 i.e. an example for this reason, wherein, and SiO ₂/ Al ₂O ₃Ratio at least 5, and go up to existing analysis to measure technology described on limit.United States Patent (USP) 3,941,871(notification number: disclosed 29,948) by crystalline porous silicates that reaction mixture produced.In this prescription, do not comprise trickle additional aluminum oxide, and showed the x-ray diffraction pattern characteristic of Z SM-5.United States Patent (USP) 4,061 No. 724 4,073, No. 865 and 4,104, has been described the aluminum oxide that tool changes and the crystalloid silicate of metal ingredient for No. 294.

Produce ether by the reaction of light olefin and low-level chain triacontanol, when being used for the supply of high octane concocting oil of gasoline with increase, needing an effective catalytic process.The ether of relatively low molecular weight as methyl-t-butyl ether (MTBE) and t-amyl group methyl ether (TAME), all within the gasoline boiling range, and is considered to have a high blending octane value.Petrochemical industry provides, molecular weight such as C ₂To C ₁Light olefin air-flow mixture, and this air-flow or its cut convert ether to, can be provided for the blending oil plant of gasoline and also can be used as the useful product of solvent.

In order to provide the existing people of ether to propose the various catalysis process that are applicable to that light olefin and low chain alkanol react.

According to United States Patent (USP) 4,042, No. 633, an available montmorillonite catalyst, optionally under the situation of additional propylene, (ZPA) makes diisopropyl ether from Virahol.

United States Patent (USP) 4,175 has disclosed the catalyst for reaction of using silicotungstic acid to generate ether as alkene and alcohol for No. 210.

As United States Patent (USP) 4,182, disclosed for No. 914, in of the operation of a kind of strong-acid cation-exchange resin of a series of uses, make DIPE by IPA and propylene as catalyzer.

United States Patent (USP) 4,418 has been described for No. 219, with iso-butylene and methyl alcohol reaction, and has borophosphoric acid, blue Tungsten oxide, or have the sial molecular ratio and be at least 12; 1 and restricted index be the crystalline aluminosilicate zeolitic of 1-12 during as catalyzer, preparation method (MTBE).

United States Patent (USP) 4,605 has disclosed with primary alconol and olefine reaction for No. 787, uses an acid zeolite as catalyzer, produces alkyl tert-alkyl oxide, as the method for MTBE and TAME.Wherein, alkene has two keys on tertiary carbon atom, and acid zeolite has the restricted index of 1-12, as, zeolite Z SM-5,11,12,23, go aluminium zeolite Y and rare earth exchanged zeolite Y.

European Patent Publication No narrated for 55, No. 045 one with alkene and alcohol reaction to generate the method for ether.For example, there are an acid zeolite such as zeolite beta, zeolite Z SM-5,8,11,12,23,35,43 and 48, when reaching other, generate MTBE with iso-butylene and methyl alcohol as catalyzer.

The invention reside in a method of producing the mixture of a kind of ether or ether.It comprises, under the etherification reaction condition, uses a kind of acid synthesizing porous crystalline zeolite with the x-ray diffraction pattern that comprises that following table 1 is listed as catalyzer, reacts with at least a alkene and at least a alcohol.

This by the ether of preceding method gained or the mixture of ether, except other usage, can also be advantageously used for the blending composition of gasoline, or be used as the cosolvent of the methyl alcohol that mixes gasoline.

The present invention can use monoene hydro carbons and mixed olefins class, (preferably at C _3-10Scope) reaction of the alcohol mixture of single alcohol (preferably have carbonatoms and reach 8, better is to have 1-4 carbonatoms).Suitable alkene has: propylene, butylene, amylene, hexene, heptene and this alkene class mixture, the waste gas of other alkene such as producer gas plant has: ethene and propylene have light olefin as the waste gas of petroleum naphtha cracker, have as fluidized catalytic cracking (FCC) petroleum naphtha: amylene, hexene and heptene and refinery FCC propane/propylene air-flow.For example, following composition is the exemplary of a FCC light olefin air-flow, and according to the present invention, it can be converted into ether:

% weight mole %

Ethane 3.3 5.1

Ethene 0.7 1.2

Propane 14.5 15.3

Propylene 42.5 46.8

Trimethylmethane 12.9 10.3

N-butane 3.3 2.6

Butylene class 22.1 18.32

Pentane class 0.7 0.4

Tertiary olefin, is used always with iso-butylene and/or uncle's amylene in this especially preferably as raw material.

Suitable alcohol has low chain alkanol as, methyl alcohol, ethanol, just-propyl alcohol, Virahol and just-butanols, and the low-level chain triacontanol that replaces is as, methoxyl group-ethanol.Equally, what must be thought over is single alcohols and alcohols mixture, and they can be obtained by the catalytic hydration reaction of alkene by known usual method.In the alcohol of suitable purposes herein, primary alconol and secondary alcohol are the most commonly used, and ethanol and methyl alcohol are particularly commonly used in this way.

As the acid synthesizing porous crystalline zeolite of catalyzer of the present invention,, have the x-ray diffraction pattern that comprises the 1 listed spectral line of tabulating down with its roasting form:

Table 1

Spacing (A) relative intensity I/I ₀* 100

12.36±0.4 M-VS

11.03±0.2 M-S

8.83±0.14 M-VS

6.18±0.12 M-VS

6.00±0.10 W-M

4.06±0.07 W-S

3.91±0.07 M-VS

3.42±0.06 VS

More particularly, comprise tabulation 2 listed spectral lines down:

Table 2

Spacing (A) relative intensity I/I ₀* 100

30.0±2.2 W-M

22.1±1.3 W

12.36±0.4 M-VS

11.03±0.2 M-S

8.83±0.14 M-VS

6.18±0.12 M-VS

6.00±0.10 W-M

4.06±0.07 W-S

3.91±0.07 M-VS

3.42±0.06 VS

Further in particular, comprise tabulation 3 listed spectral lines down:

Table 3

Spacing (A) relative intensity I/I ₀* 100

12.36±0.4 M-VS

11.03±0.2 M-S

8.83±0.14 M-VS

6.86±0.14 W-M

6.18±0.12 M-VS

6.00±0.10 W-M

5.54±0.10 W-M

4.92±0.09 W

4.64±0.08 W

4.41±0.08 W-M

4.25±0.08 W

4.10±0.07 W-S

4.06±0.07 W-S

3.91±0.07 W-VS

3.75±0.06 W-M

3.56±0.06 W-M

3.42±0.06 VS

3.30±0.05 W-M

3.20±0.05 W-M

3.14±0.05 W-M

3.07±0.05 W

2.99±0.05 W

2.82±0.05 W

2.78±0.05 W

2.68±0.05 W

2.59±0.05 W

The most specifically be to say, baked zeolite has the x-ray diffraction pattern of the spectral line that comprises following tabulation 4.

Table 4

Spacing (A) relative intensity I/I ₀* 100

30.0±2.2 W-M

22.1±1.3 W

12.36±0.4 M-VS

11.03±0.2 M-S

8.83±0.14 M-VS

6.86±0.14 W-M

6.18±0.12 M-VS

6.00±0.10 W-M

5.54±0.10 W-M

4.92±0.09 W

4.64±0.08 W

4.41±0.08 W-M

4.25±0.08 W

4.10±0.07 W-S

4.06±0.07 W-S

3.91±0.07 M-VS

3.75±0.06 W-M

3.56±0.06 W-M

3.42±0.06 VS

3.30±0.05 W-M

3.20±0.05 W-M

3.14±0.05 W-M

3.07±0.05 W

2.99±0.05 W

2.82±0.05 W

2.78±0.05 W

2.68±0.05 W

2.59±0.05 W

These data record with standard technique.Radiation is the K-α of red copper dual (spectrum) line, and has used the diffractometer that scintillometer is housed and uses the counter that is attached thereto.Peak height, I and as the position of 2 theta functions are used the algorithm on the counter that links with diffractometer to record, and θ is a Bragg angle herein.By these relative intensities, 100 I/Io, wherein, Io is the intensity of intense line or peak value, and α (observed value) be with (

) be the spacing of unit representation, and to be recorded also corresponding to the record spectral line, in table 1-4, relative intensity is pressed mark: W-Weak, and M-medium, S-Strong and VS-Very Strong provide.According to the intensity classification, can roughly be defined as follows:

W＝0-20

M＝20-40

S＝40-60

V S＝60-100

Can think that these x-ray diffraction patterns are features of all existing crystal compositions.Sodium shape and other positively charged ion shape have been disclosed in the variation of spacing and relative intensity, exist identical in fact figure line and some accessory skews.Other accessory variation can be according to Y to the relation of X and take place, as, silicon to aluminium, the mol ratio of its specific sample, with and heat treatment degree.

The zeolite that is used as the catalyzer in his reaction process of ether among the present invention contains the composition of following molar relationship:

X ₂O ₃＝（n）YO ₂，

Wherein, X is a trivalent element, as aluminium, and boron, iron and/or gallium, aluminium preferably, Y is a quadrivalent element, as silicon and/or germanium, preferably silicon.N is at least 10, is generally 10～150, and commonly used is 10～60, and more commonly used is 20～40.Under synthesized form, zeolite has following, with the YO with oxide molar number/several mole of anhydride as the basis ₂The chemical formula of expression:

（0.005-0.1）Na ₂O：（1-4）R：X ₂O ₃＝nYO ₂

Wherein, R is an organic composition.Na and R composition are present in the crystallisation process because of them, and get in touch with zeolite facies, and can below post crystallization method and easily being removed in greater detail.

Come compared with similar crystalline structure, zeolite used herein is to thermally-stabilised, and shown that higher surface area (by BET(Bruenauer, Emmet and Teller) test records greater than 400m ²/ gm) and unusual big adsorptive power.Particularly, this zeolite has shown for hexanaphthene steam greater than 4.5%(weight) the equilibrium adsorption value, and for just/-hexane steam greater than 10%(weight) the equilibrium adsorption value.Show that by above-mentioned chemical formula this zeolite is synthesized with the Na positively charged ion hardly.Thereby it can be used as the acid active catalyzer that has in a kind of etherification reaction, and need not an exchange process.But, within the ideal scope, the sodium cation of synthetic form material originally can be replaced by this field known technology, and at least, the ion-exchange of use is partly replaced by other positively charged ion.Wish that the metathetical positively charged ion comprises metal ion, hydrogen ion, the precursor of hydrogen is as ammonium and ion and mixture.

Before using as the catalyzer of etherification reaction, this zeolite should carry out heat treated, removing wherein part, or whole any organic components.

The zeolite etherificate urges agent also to can be used for having with another the combining closely of composition of etherificate catalytic activity herein, as, above mentioned arbitrary known catalysts.

Before being used for etherification reaction process of the present invention, this zeolite is answered, and is dehydrated at least in part.This dehydration can be at an inert atmosphere, and in air, nitrogen etc., with normal atmosphere, be lower than a normal atmosphere or superatmospheric pressure power, the temperature range 30 minutes that crystal is heated to 200 ℃～595 ℃ was finished by 48 hours.Dehydration also can at room temperature only be placed in this crystalline material in one valve tube and carry out.But, at this moment, need long time to obtain enough dehydrating amounts.

Zeolite used in the inventive method can make from a reaction mixture.This reaction mixture comprises: as the raw material of cationic alkali such as sodium or potassium or alkaline-earth metal (M), oxide compound as the trivalent element X of aluminium, oxide compound as quadrivalent element Y such as silicon, organic (R) alignment agent and the water of hexamethylene imine form, this reaction mixture has a composition of representing with oxide mol ratio, and the oxide mol ratio scope is as follows:

Reactant can be with commonly used

YO ₂/X ₂O ₃10-60 10-40

H ₂O/YO ₂5-100 10-50

OH/YO ₂0.01-1.0 0.1-0.5

M/YO ₂0.01-2.0 0.1-1.0

R/YO ₂0.05-1.0 0.1-0.5

In synthetic method preferably, YO ₂Reactant comprises the solid YO of a suitable volume ₂, for example, at least about 30%(weight) solid YO ₂YO herein ₂Be silicon-dioxide, silica material comprises 30%(weight at least) solid silica, as sedimentary, spray-dired silicon-dioxide of Ultrasil(, comprise 90%(weight) silicon-dioxide) or one of Hi Sil(comprise 87%(weight) SiO ₂, 6%(weight) free moisture content and 4.5%(weight) hydration in conjunction with moisture content, and have the silicon-dioxide that the sedimentary water of 0.02 micron particle contains).Use such silica material to help crystal formation from said mixture.If another kind of raw silicon oxide material contains about 28.8%(weight as one kind of Q-Brand() SiO ₂, 8.9%(weight) Na ₂O and 62.3%(weight) H ₂The water glass of O) be used, then crystallization reaction does not almost produce required zeolite, and may produce the impurity phase as other crystalline structure of Z SM-12.Thereby, best, this YO ₂, comprise weight at least about 30%(as silica material) and solid-state YO ₂, as SiO ₂, more preferably comprise weight at least about 40%() solid-state YO ₂As SiO ₂

Crystallization reaction can be in a suitable reaction vessel, as, polypropylene vial in autoclave teflon lined or stainless, is carried out under static or agitation condition.The crystallization reaction temperature is generally 80 ℃～225 ℃, and 25 hours to 60 days time, after this crystal is isolated from liquid and reclaimed.

As have at least 0.01% seed crystal (according to gross weight) of crystalline product, then crystallization reaction is convenient to carry out, and reaches 0.1% easier carrying out as the seed crystal ratio, as the seed crystal ratio reach 1% best.

Before being used for method of the present invention, the zeolite of generation may combine with another kind of material, and this material can stand temperature used in the etherification procedure of the present invention and other condition.These materials include activity and inert material, the zeolite of synthetic or natural generation, and inorganic materials such as clay, metal oxides such as silicon-dioxide and/or aluminum oxide.The latter promptly can be natural resultant, also can be gelatinous precipitate or the gel form as the mixture of silicon-dioxide and metal oxide.Locate therewith said zeolite in conjunction with the time, a kind of use of material may change transformation and/or its selectivity of this catalyzer, this kind material in zeolite synthetic with it in conjunction with or have and itself tool catalytic activity.Inert material can be used as suitable diluent control inversion quantity, and like this, ether product can regularly obtain, and need not other means go to control speed of reaction economically.These materials can be impregnated in the clay of natural generation, as wilkinite and kaolin, to improve under the etherification reaction operational condition of commercial production scale the crushing strength of catalyzer.Said material, i.e. clay, oxide compounds etc. have played binding agent to catalyzer, and general hope can provide the catalyzer of the high crushing strength of a kind of tool, because in plant-scale application, wishes to prevent that catalyzer is fractured into powder-material here.These clay adhesives also just are used for the crushing strength of improving catalyzer.

Those energy quilts natural generation clay of combination of zeolites herein comprise: polynite and kaolin group.Kaolin group comprises inferior wilkinite again, and the kaolin same clan is construed to Dixie again usually, Mc Namee, Georgia. and Florida and other.Wherein, the essential mineral composition has: halloysite, kaolinite, dickite, nakrite or anauxite.The raw material form of these clays after can original exploitation used, or at first handles through roasting, acid treatment or chemical modification.The tackiness agent that is used for combined zeolite also comprises inorganic oxide, especially aluminum oxide.

Except above-mentioned materials, zeolite herein also can make up with porous matrix material, as silica-alumina, and silica-magnesia, silicon-dioxide-zirconium white, silica-thorium oxide, silica-beryllia, silica-titania, and tertiary mixture as, silica-alumina-Thorotrast, silica-alumina-zirconium white, silica-alumina-magnesium oxide and silica-magnesia-zirconium white.It also can provide at least a portion above-mentioned body material with colloidal form effectively, to promote extruding of this bonding catalyst composition.

The relative proportion variation range of zeolite and inorganic oxide matrix material is very big, and crystalline content is from 1-90%(weight), more commonly used, be when carrying out especially with particle when mixing, crystalline content is the 2-80%(weight of composition).

The stability of etherification reaction catalyzer of the present invention can increase by steam method.When gas steams, generally be by zeolite and for example 5-100% under at least 300 ℃ of temperature (being preferably 300-650 ℃), the contact of the steam of pressure 101-2500KPa, decatize at least 1 hour (preferably 1-200 hour) is finished.In embodiment more specifically, can make this catalyzer stand decatize: steam 75-100%, 315 ℃～500 ℃ of temperature, under the normal atmosphere, 2-25 hour.

The operational condition of etherification reaction process herein is not harsh especially.It still can comprise following condition: temperature 20-200 ℃, and comparatively ideal is 50-160 ℃, it would be desirable 60-120 ℃; Total system pressure is a 100-20260KPa(1-200 normal atmosphere), comparatively ideal is 300-8100KPa(3-80 normal atmosphere), it would be desirable 1000-1520KPa(10-15 normal atmosphere); Alcohol is 0.1～5 with the mol ratio of alkene, and more satisfactory is 0.2～2, and it would be desirable 0.5～1.2.

Etherification reaction process of the present invention can intermittent type and continuous mode, and with a stirred-tank reactor or flow reactor of fixed bed, with liquid phase, vapour phase or vapour-liquid mixed phase condition are carried out.Used flow reactor has, trickle bed formula, liquid upper reaches flowing-type, the dirty flowing-type of liquid, counter-current flow formula and concurrent flow formula etc.Carry out WH SV(gram alkene/hour gram zeolite when reacting intermittent type) be 0.01～200 o'clock, the reaction times is 20 minutes～20 hours.If be suitable for operate continuously, comparatively ideal is WH SV0.5～50, is more preferably 1～30.Usually, wish to reclaim all unreacted alkene and/or alcohol, and make it be recirculated into reactor.

Etherification reaction process of the present invention will be described in more detail with reference to following embodiment and accompanying drawing.

In the accompanying drawing, Fig. 1-5 is respectively the x-ray diffraction pattern of crystalline material product of the roasting of embodiment 1,3,4,5 and 7.

In these embodiments, adsorpting data is listed, with water, the sorptive power masterpiece one of hexanaphthene and/or just-hexane is relatively.These data are the equilibrium adsorption value of following mensuration.

A baked sorbent material sample of weighing in an adsorption chamber, contacts with the pure adsorbate steam of an ideal.This adsorption chamber is evacuated to less than the 1mm mercury column.Then, this baked sorbent material sample and 1.6KPa(12mm mercury column) water vapour or 5.3KPa(40mm mercury column) just-hexane or 5.3KPa(40mm mercury column) hexanaphthene steam contact the vapor-liquid equilibrium pressure of pressurization each adsorbate during less than 90 ℃.This pressure is kept constant (within ± 0.5mm mercury column scope) by the adsorbate steam that adds pressurestat control in adsorption cycle, this adsorption cycle is no more than 8 hours.When adsorbate is adsorbed by crystalline zeolite, the minimizing of pressure causes pressurestat to open valve, makes more adsorbate steam enter adsorption chamber, recovers above-mentioned control pressure.When pressure change is not enough to start pressurestat, adsorption is promptly accused and is finished.The adsorptive power of the g/100g sample of roasting sorbent material is made in the increase of weight by meter.Zeolite used herein has also shown for hexanaphthene steam greater than 4.5%(weight), be generally weight greater than 7.5%() the equilibrium adsorption value, for just-hexane steam is greater than 10%(weight), for water vapor greater than 10%(weight) the equilibrium adsorption value.

When detecting the α value, can notice that this α value is one with standard catalyst, the approximate index of the catalytic cracking activity of the catalyzer of making comparisons, simultaneously, it has provided relative response velocity constant (the hexane conversion rate of per volume of catalyst unit time).Be taken as 1(reaction velocity constant=0.016 second based on the α value of highly active silica-alumina cracking catalyst ^-1).Alpha test used herein is described in J.Catalysis, and 61, pp.390-396(1980).It should be noted that for specific crystalline silicate catalyst the original speed constant of many acid catalyzed reactions is proportional to this α value.As the disproportionation speed of toluene, the isomerization speed of dimethylbenzene, conversion of olefines and methanol conversion speed.(seeing " The Active Side of Acidic Aluminosilicate Catalysts " Neture, Vol.309, No.5969, pp.589-591,14 June 1984).

Embodiment 1

1 part of sodium aluminate (43.5%Al ₂O ₃, 32.2%Na ₂O, 25.6% H ₂O) be dissolved in one and comprise 1 part of 50%NaOH solution and 103.13 parts of H ₂In the solution of O.Add 4.50 parts hexamethylene imines.Add 8.55 parts Ultrasil to generating solution, a kind of sedimentary, spray-dired silicon-dioxide (about 98%SiO ₂).

The composition of the following mol ratio of reaction mixture tool:

SiO ₂/Al ₂O ₃＝30.0

OH/SiO ₂＝0.18

H ₂O/SiO ₂＝44.9

Na/SiO ₂＝0.18

R/SiO ₂＝0.38

Wherein:

R is a hexamethylene imines.

This mixture is in crystallization 7 days in the stainless steel reactor that a band stirs under 150 ℃.Filtering for crystallizing product, washing and 120 ℃ of following dryings.After 20 hours 538 ℃ roasting, this X-ray diffraction pattern promptly contains the listed main spectral line of table 5.The x-ray diffraction pattern of roasting product for this reason shown in Figure 1.The adsorptive power of this roasting material is after measured:

H ₂O 15.2%(weight)

Hexanaphthene 14.6%(weight)

Just-hexane 16.7%(weight)

The surface-area of this roasting crystalline material is 494m after measured ²/ g.

Chemical constitution without the roasting material is as follows:

Composition %(weight)

SiO ₂66.9

Al ₂O ₃5.40

Na 0.03

N 2.27

Ash content 76.3

SiO ₂/ Al ₂O ₃Mole ratios 21.1

Table 5

Number of degrees 2-θ spacing (A) I/I ₀

2.80 31.55 25

4.02 21.98 10

7.10 12.45 96

7.95 11.12 47

10.00 8.85 51

12.90 6.86 11

14.34 6.18 42

14.72 6.02 15

15.90 5.57 20

17.81 4.98 5

20.20 4.40 20

20.91 4.25 5

21.59 4.12 20

21.92 4.06 13

22.67 3.92 30

23.70 3.75 13

24.97 3.57 15

25.01 3.56 20

26.00 3.43 100

26.69 3.31 14

27.75 3.21 15

28.52 3.13 10

29.01 3.08 5

29.71 3.01 5

31.61 2.830 5

32.21 2.779 5

33.35 2.687 5

34.61 2.592 5

Embodiment 2

The part of the roasting crystalline product of embodiment 1 is through testing with the alpha test method, and recording its α value is 224.

Embodiment 3-5

Three kinds of other synthesis reaction mixtures of branch are produced by component shown in the table 6.This mixture is by sodium aluminate, sodium hydroxide, and Ultrasil, hexamethylene imines (R) and water make.Under spontaneous pressure, this mixture is stored in 150 ℃ of temperature, 143 ℃ and 150 ℃ respectively in the stainless steel pressure pan be 7 days, 8 days and 6 days.Solids is formed with unreacted after filtration and is separated, with after washing, and dry down at 120 ℃.This product crystal is passed through X-ray diffraction, absorption, surface-area and chemical analysis then.Its analytical results is also listed in table 6, and its diffraction pattern is shown in Fig. 2,3 and 4 respectively.The test of absorption and surface-area is for roasting product.

Table 6

Embodiment 345

Synthetic mixture, molar ratio

SiO ₂/Al ₂O ₃30.0 30.0 30.0

OH/SiO ₂0.18 0.18 0.18

H ₂O/SiO ₂19.4 19.4 44.9

Na/SiO ₂0.18 0.18 0.18

R/SiO ₂0.35 0.35 0.35

Product component %(weight)

SiO ₂64.3 68.5 74.5

Al ₂O ₃4.85 5.58 4.87

Na 0.08 0.05 0.01

N 2.40 2.33 2.12

Ash content 77.1 77.3 78.2

SiO ₂/ Al ₂O ₃Molar ratio 22.5 20.9 26.0

Absorption %(weight)

H ₂O 14.9 13.6 14.6

Hexanaphthene 12.5 12.2 13.6

N-hexane 14.6 16.2 19.0

Surface-area m ²/ g 481 492 487

Embodiment 6

The amount of embodiment 3,4 and 5 roasting (538 ℃, 3 hours) crystalline silicate product records its α value and is respectively 227,180 and 187 with the test of alpha test method.

Embodiment 7

For the further preparation method of this kind zeolite is described, 4.49 parts of hexamethylene imines is added to one comprises 1 part of sodium aluminate, 1 part of 50%NaOH solution and 44.19 parts of H ₂Go in the solution of O.This mixed solution is added 8.54 parts of Ultrasil silicon-dioxide again.This mixture is stirred 59 hours and crystallization under 145 ℃, last resultant is washed, and 120 ℃ of dryings.

Product X-ray diffraction with drying crystalline is illustrated in Fig. 5, and confirms that this product is a crystalline material of the present invention.The product chemical ingredients, surface-area and adsorption analysis the results are shown in table 7:

Table 7

Product is formed (not roasting) %(weight)

C 12.1%(weight)

N 1.98%(weight)

Na 640ppm

Al ₂O ₃5.0%(weight)

SiO ₂74.9%(weight)

SiO ₂/ Al ₂O ₃Molar ratio 25.4

Absorption %(weight)

Hexanaphthene 9.1

Just-hexane 14.9

H ₂O 16.8

Surface-area m ²/ g 479

Embodiment 8

25 grams are by the solid crystal product of embodiment 7 gained, in 538 ℃ flowing nitrogen atmosphere by roasting 5 hours, subsequently with 5% oxygen 538 ℃ of following purges 16 hours.

Learn from else's experience material sample 3 gram of roasting is with TEABr, TPABr and the LaCl of the 0.1N of 100ml ₃Solution carries out ion-exchange respectively.Every kind of exchange was at room temperature carried out 24 hours and triplicate.Exchange back product is collected with filtration method, and after being washed to non-halogen thing, drying.The composition of the sample after this exchange is shown in following table, and it has shown that silicate crystal is to the exchange capacity of different ions herein.

Exchange ion TEA TPA La

Ion is formed %(weight)

Na 0.095 0.089 0.063

N 0.30 0.38 0.03

C 2.89 3.63 -

La - - 1.04

Embodiment 9

Be sized order by embodiment 8 gained lanthanums (La)-exchange sample into 14-25, then in 538 ℃ air by roasting 3 hours.This roasting material α value is 173.

Embodiment 10

By embodiment 9 gained through lanthanum (the La)-exchange material sample of roasting under 649 ℃, with the rapid decatize of 100% steam 2 hours.Through the sample α of decatize value is 22, and has shown that this zeolite has good stability in rapid hydrothermal treatment consists.

Embodiment 11

It is the preparation method of the zeolite of boron that this example has described this X that is in the above-mentioned general formula in detail.Boric acid is added to for 2.59 parts contains 1 part of 45%KOH solution and 42.96 parts of H ₂In the solution of O.Add 8.56 parts of Ultrasil silicon-dioxide again, thoroughly this mixture of homogenizing.Add 3.88 parts of hexamethylene imines again to this mixed solution.

The following mol ratio of this reaction mixture tool is formed:

SiO ₂/B ₂O ₃＝6.1

OH/SiO ₂＝0.06

H ₂O/SiO ₂＝19.0

K/SiO ₂＝0.06

R/SiO ₂＝0.30

R is a hexamethylene imines herein.

This mixed solution in-stainless steel reactor, under 150 ℃ to stir 8 days by crystallization.After this crystalline product is filtered, washes, 120 ℃ of oven dry.Portioned product is found the following adsorptive power of tool through 540 ℃ of roastings 6 hours:

H ₂The O(12 mmhg) 11.7%(weight)

Hexanaphthene (40 mmhg) 7.5%(weight)

Just-ethane (40 mmhg) 11.4%(weight)

The surface-area of this roasting crystalline material is 405m after measured ²/ g.

Unfired materials chemistry is composed as follows:

N 1.94%(weight)

Na 175ppm

K 0.60%(weight)

Boron 1.04%(weight)

Al ₂O ₃920ppm

SiO ₂75.9%(weight)

Ash content 74.11%(weight)

SiO ₂/ Al ₂O ₃Mol ratio=1406

SiO ₂/ (Al+B) ₂O ₃, mol ratio-25.8

Embodiment 12

By embodiment 11 gained partial roasting crystalline products through NH ₄After Cl handles, roasting once more.Last crystalline product is with the test of alpha test method, and recording its α is 1.

Embodiment 13

This embodiment has illustrated that the X in the above-mentioned general formula is another preparation method of the zeolite of boron.2.23 parts boric acid adding is contained 1 part 50% NaOH solution and the solution of 73.89 parts of HO, add 15.29 parts Hi Sil silicon-dioxide again, and 6.69 parts hexamethylene imines subsequently.This reaction mixture has the composition of following mol ratio:

SiO ₂/B ₂O ₃＝12.3

OH/SiO ₂＝0.056

H ₂O/SiO ₂＝18.6

K/SiO ₂＝0.056

R/SiO ₂＝0.30

Wherein, R is a hexamethylene imines.

This mixture in stainless steel reactor, 300 ℃ of temperature, crystallization to stir 9 days.This crystalline product is filtered, and washing is again with 120 ℃ of oven dry.This adsorptive power through the roasting material is (6 hours 540 ℃) after measured:

H ₂O 14.4%(weight)

Hexanaphthene 4.6%(weight)

Just-hexane 14.0%(weight)

This surface-area through the roasting crystalline material is 438m after measured ²/ g.

Chemical constitution without the roasting material is after measured:

Composition %(weight)

N 2.48

Na 0.06

Boron 0.83

Al ₂O ₃0.50

SiO 73.4

SiO ₂/ Al ₂O ₃Mol ratio=249

SiO ₂/ (Al+B) ₂O ₃Mol ratio=28.2

Embodiment 14

Tested through the alpha test method through the crystalline product of roasting by embodiment 13 gained part, recording its α value is 5.

Embodiment 15-43

These examples have compared the catalyst for etherification performance of three kinds of zeolites: Si/Al ₂O ₃Mol ratio is about 70: 1 Z SM-5(embodiment 15-25), Si/Al ₂O ₃Mol ratio is about 6: 1 USY(embodiment 26-33), and Si/Al of the present invention ₂O ₃Mol ratio is about 26: 1 zeolite (embodiment 34-43).Zeolite of the present invention can contain 1.00 parts sodium aluminate, 1.00 parts 50%NaOH by 4.49 parts hexamethylene imines is added to.8.54 the mixed solution of the deionized water of part Ultrasil UN3 and 44.19 parts.This reaction mixture is heated to 143 ℃ (290 °F), and under this temperature, stirs with crystallization in a pressure pan.After reaching complete crystallization, wherein the major portion of hexamethylene imines is removed from pressure pan with the distillation that control is arranged, and zeolite crystal separates with after the washing of deionized water by filtering with raffinate, drying.This zeolite crystal of a part and Al ₂O ₃In conjunction with, form the zeolite of 65 weight parts and the Al of 35 weight parts ₂O ₃Mixture.This mixture is added entry, generate catalyzer formation extrusion moulding mixture so that make.The roasting 6 hours in the nitrogen of 540 ℃ (1000) of this catalyzer, with after the exchange of moisture ammonium nitrate and in the air of 540 ℃ (1000) roasting be activated in 6 hours.

In all these examples, methyl alcohol and iso-butylene or isopentene are imported into upper reaches flowing-type fixed-bed reactor with different space velocity (2～200).This reactor is equipped with above-mentioned a kind of, is diluted to about 10%(volume with sand) with the zeolite of maintenance constant volume.

Reaction conditions among each embodiment and the results are shown in table 8,9 and 10:

The activity of three kinds of catalyst for etherification of making comparisons in embodiment 15-43 is carried out quantitatively with following formula:

In（1- (X)/(Xeq) ）＝- (K)/(Xeq) 1/(WHSV)

Wherein, K is pseudo-one-order velocity constant, and X is an olefin conversion, and the equilibrium conversion of Xeq under above-mentioned ether reaction conditions is to iso-butylene, and empirical value is 93%, is 51% to isopentene.The Model for etherification kinetics that three kinds of zeolite catalysts are done relatively is listed in the table below 11:

Table 11

The Model for etherification kinetics of zeolite catalyst relatively

Reaction rate constant performance ratio (PR)

Embodiment zeolite catalyst mole/hour, the gram catalyzer (TAME)/(MTBE) * 100

MTBE TAME

15-25 ZSM-5 0.21 0.014 6.7

26-33 USY 0.01 0.003 30

34-43 the present invention 0.16 0.032 20

In the table 11, performance ratio (PR) is quantitative ratio, this ratio are isopentene with respect to the methanol consumption of iso-butylene than in the processing of parallel feeding, generally wish this ratio at least 10, more preferably greater than 15.Ratio 100 expressions, no matter carbonatoms is low or high, alkene all tends to be consumed with a comparable ratio.In three zeolite catalysts, the USY tool is TAME/MTBE performance ratio preferably.But, the reaction velocity constant to USY has shown that this activity of such catalysts is very low.And Z SM-5 and catalyzer of the present invention have acceptable greater activity.Yet conversely, catalyzer of the present invention shown in its performance ratio, has ability excellent, that good activity and ideal selective binding are got up.

These embodiment have illustrated according to the present invention, use 65%(weight) and 35%(weight) aluminum oxide (tackiness agent), make catalyzer, the preparation method of Ethyl Tertisry Butyl Ether (ETBE).This ETBE except other usage, also can be used as the high octane concocting oil of gasoline.

Among each embodiment, the condition of ethanol and isobutene reaction and gained the results are shown in as following table 12.

Table 12

Conversion condition embodiment

44 45 46

Decatize hours 235

Temperature ℃ 100 101 101

Pressurization pound/inch KPa) 210(1549 210(1480 200(1480)))

Mol ratio 1.98 1.98 2.05

Alkene 5.91 5.91 12.24

Conversion % based on product

Ethanol 5.0 8.1 3.7

Iso-butylene 12.1 17.4 7.0

Product is formed %(weight)

Iso-butylene 29 30 36

Ethanol 63 59 59

ETBE 7 12 5

Other ^*＜0.5＜0.5＜0.5

^*These other materials may be mixed with impurity when charging.

Claims (12)

1, the manufacture method of the mixture of a kind of ether or ether, it is characterized in that it comprises with at least a alkene and at least a alcohol, under the etherification reaction condition, react, and using the synthesizing porous crystalline zeolite of a kind of acidity as catalyzer, this zeolite has the X-ray diffracting spectrum of the listed spectral line of table 1 in the specification sheets.

2, method according to claim 1 is characterized in that, said zeolite has the X-ray diffracting spectrum of the listed spectral line of table 2 in the specification sheets.

3, method according to claim 1 is characterized in that, said zeolite has the X-ray diffracting spectrum of the listed spectral line of table 3 in the specification sheets.

4, method according to claim 1 is characterized in that, said zeolite has the X-ray diffracting spectrum of the listed spectral line of table 4 in the specification sheets.

5, according to arbitrary described method among the claim 1-4, it is characterized in that said zeolite has: concerning hexanaphthene steam greater than 4.5%(weight) and for just-hexane steam greater than 10%(weight) the equilibrium adsorption ability.

6, according to arbitrary described method among the claim 1-4, it is characterized in that said zeolite has the composition that comprises following molar relationship:

X ₂O ₃＝（n）YO ₂

Wherein, n is at least 10, and X is a trivalent element and Y is a quadrivalent element.

7, method according to claim 6 is characterized in that, said X comprises aluminium and Y comprises silicon.

According to arbitrary described method among the claim 1-4, it is characterized in that 8, said alkene has 3-10 carbon atom.

9, method according to claim 8 is characterized in that, said alkene is iso-butylene or isopentene.

10, method according to claim 8 is characterized in that, said alcohol has until 8 carbon atoms.

11, method according to claim 9 is characterized in that, said alcohol is methyl alcohol, ethanol, n-propyl alcohol, Virahol or butanols, or the mixture of above-mentioned alcohol.

According to arbitrary described method among the claim 1-4, it is characterized in that 12, said etherification reaction condition comprises: 20-200 ℃ temperature, 100-20260KPa(1-200 normal atmosphere) total system pressure and the alkene of 0.1-5 to the mol ratio of alcohol.

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