CN85103846A - Titanium-silicate compositions - Google Patents

Abstract

Find that titanium-silicate compositions can be used as molecular sieve and can be used as the hydrocarbon conversion and the catalyst composition of other technical process.Under anhydrous situation, the unit experience of molecular sieve becomes:

MR:(Ti _xSi _y) O ₂Wherein " R " represents at least a organic formwork agent; " m " represents every mole of (Ti _x, Si _y) O ₂" R " mole number, and " x " and " y " represents the titanium that exists as tetrahedral oxide and the molar ratio of silicon respectively.

Description

Titanium-silicate compositions

The technical field of the invention

The invention relates to novel combination of molecular sieve, these compositions contain titanium and the silicon with tetrahedral oxide units skeleton structure form.These compositions carry out hydrothermal treatment consists to the reaction mixture that contains active titanium source, silicon and oxygen and preferably contain at least a organic formwork agent and make.

Discussion about molecular sieve

The people who is familiar with sieve technology knows that molecular sieve has the crystalline structure and is the silico-aluminate type.Both there had been natural generation, and had the synthesizing Si-Al hydrochlorate again, and reported the molecular sieve that several kinds are so really in the document.

Though it is people know a few kind pure aluminium silicate (molecular sieve of binary), fewer about other the report with the ternary molecular sieve of binary.And about the report of the ternary molecular sieve that contains titanium component still less, in titaniferous those examples of report, the titaniferous amount in molecular sieve is less, titanium or exist or exist with the form of surface improver with sedimentary form.

What a early stage report crystallization titanium-silicate boiled face (certainly, such face that boils of the not now common usefulness of these compositions) is United States Patent (USP) 3,329,481.United States Patent (USP) 3,329, the chemical formula of 481 disclosed crystalline titanium-silicate is:

D is the monovalence metal in the formula, divalent metal, and ammonium ion or hydrogen ion, " n " they are the valence mumbers of D, " X " is that digital 0.5-3 and y are digital 1.0-3.5 approximately.The boil feature of X-ray powder diffraction spectrogram of face of these crystallization titanium-silicate is all to comprise the d-spacing that is selected from one of following one group of spectrogram:

Spectrogram A: spectrogram B: spectrogram C:

7.6-7.9A ⁰4.92±0.04A ⁰2.82±0.03A ⁰

3.2±0.05A ⁰3.10±0.04A ⁰1.84±0.03A ⁰

United States Patent (USP) 3,329,481st is with an alkali metal salt (M of IV-B family peroxy acid ₄* O ₆) or their water contain thing and prepare titanium-silicate as " key reagents " (the 3rd hurdle, 17 row and following or the like).

United States Patent (USP) 4,358,397 disclosed improved silico-aluminates prove that it is difficult will obtaining titaniferous composition.Use titanium, one or more element derived compounds in zirconium or the hafnium are handled silico-aluminate can improve silico-aluminate.It is said that formed composition contains the oxide compound than these elements of small proportion.Obviously, in the composition of introducing, the oxide compound of titanium, zirconium or hafnium is the form with the oxide compound of deposit, and is to exist with less ratio.

As mentioned above, though in patent documentation and the document delivered, silico-aluminate has been carried out discussing widely,, recently, except these materials, few of about the utilizable information of aluminate or phosphate.This is real especially in the field of titaniferous composition.Titaniferous combination of molecular sieve (to such an extent as to wherein titanium is to exist or the physics and/or the chemical property of so closely related change molecular sieve with framework of molecular sieve) also is provided with report widely.As mineralogy magazine (Mineralogical Magazine) Vol37 in September, the paper " Ti in silicate of №, 287, the 366～399 pages (1969) ⁴⁺Can replace Si ⁴⁺? " specified, this is understandable for the problem of discussion silico-aluminate.In this piece paper, its conclusion is because titanium is to be better than the combination of octahedra ground, rather than the combination of tetrahedron ground, is impossible so replace framework silicon by titanium in silico-aluminate.As United States Patent (USP) 3,329,481 disclosedly and discussed above like that also form crystallization " silicotitanate boil face ", have wherein formed a kind of metal-silicon hydrochlorate complex compound, and have obtained the silicotitanate product through handling.The evidence of the silicotitanate claimed is based on the data of X-ray powder diffraction spectrogram, about whether this just represents that titanium substitutes onto in the silicate skeleton structure, these data are somewhat suspicious, because zirconium silicate is also observed the same X-ray diffraction spectrogram of being claimed.And, reported that about the pure silicon molecular sieve similarly x-ray diffraction pattern figure shows that similar spacing (two numerical value among the spectrogram B) is (referring to English Patent 2,071,071A).

The English Patent 2,071 that on December 21st, 1979 announced discloses titanium and has been mixed in the structure of pure silicon molecular sieve type among the 071A.It claims that the amount that substitutes onto titanium in the pure silicon molecular sieve type structure is considerably less, is not more than the mole number of 0.04 mole of %(based on titanium dioxide silicon), and may hang down to 0.0005.In the example of any report, the chemical method assay determination of the content of titanium, and also the value of measuring is greater than 0.023.By comparing English Patent 2,071, Fig. 1 a among the 071A and Fig. 1 b, the amount that shows existing titanium is so few, to such an extent as to do not observe the obvious variation of the X-ray diffraction spectrogram of pure silicon molecular sieve, and owing to be mingled with titanium dioxide, viewed this small variation may be very simple and clear.Owing to lack other analytical data, thus can not good explanation English Patent 2,071, the result of 071A.To titanium dioxide, comparative data is not disclosed.

April 27 nineteen eighty-three disclosed invalid european patent application book No.82109451.3(publication number 77,522) further illustrate the difficulty that is run in the titaniferous combination of molecular sieve process in preparation.The exercise question of this piece application for patent is " titaniferous zeolite and their production method and the purposes of above-mentioned zeolite ", is actually to preparing titaniferous combination of molecular sieve.Though the applicant claims the titanium silico-aluminate of preparation five silicon ring structures are arranged, obviously it is the conclusion that is obtained by the product in the analysis example.In these examples, in the molecular sieve that five silicon ring structures are arranged, titanium is not that the form with the tetrahedral oxide of skeleton structure exists.The product of the example of european patent application book No.82109451.3 will go through in comparative example thereafter.

Brief description of drawings

Fig. 1 is the scanning electron microscope diagram (SEM) of the product among the european patent application book No.82109451.3.

General introduction of the present invention

The invention relates to new combination of molecular sieve, these compositions have TiO ₂And SiO ₂The three-dimensional microporous crystal skeleton structure of tetrahedral oxide unit.These new molecular sieves have a unit empirical formula (representing with moisture-free basis):

mR∶（Ti _xSi _y）O ₂

" R " representative is present in a kind of organic formwork agent in the pore system in the crystal in the formula; " m " represents every mole of (Ti _xSi _y) O ₂The mole number of middle " R " that exists, its value is 0-about 0.3; " X " and " y " represents the titanium that exists with the tetrahedronal oxide of skeleton unit and the molar fraction of silicon respectively.The value of " X " and " y " is usually greater than 0.01, and less than 0.99, X+y=1 and be such: when (1) characterized when the X-ray spectrogram with the table III, " y " was less than 0.9615, and " X " is greater than 0.0385; (2) when the X-ray spectrogram with the table VII characterizes, " X " and " y " all greater than 0.01 less than 0.99; Or (3), " y " greater than 0.7776, less than 0.9615, or less than 0.05, and " X " greater than 0.0385 less than 0.2224 with greater than 0.5.

Titanosilicate group product thing of the present invention generally is written as " TiSO " here, and " TiSO " represents molecular sieve of the present invention, and these molecular sieves have TiO ₂And SiO ₂The skeleton structure of tetrahedral oxide units.The material of specific type will be differentiated by the material of the different structure be named.Give the selected number of material of these different structures, these materials just form TiSO family, and therefore note is made " TiSO-i ", and the number in " TiSO-i " " i " is an integer.This representation is the structural relation that a kind of empirical method ， And and not planning represents the material that characterizes with other also available numbering system.

Detailed description of the present invention

The invention relates to the titanosilicate molecular sieve, this molecular sieve analog has TiO ₂And SiO ₂The three-dimensional micropore crystallization skeleton structure of tetrahedron element, these skeleton structures have unit empirical formula (representing with moisture-free basis):

mR∶（Ti _xSi _y）O ₂（1）

At least a organic formwork agent that is present in the crystal endoporus system of " R " representative in the formula; " m " represents every mole of (Ti _xSi _y) O ₂In the mole number of existing " R ", it is worth between 0 and about 0.3, maximum value in each case depends on the molecular size of template and the useful micro pore volume of special TiSO molecular sieve; The value of " X " and " y " is usually greater than 0.01, and less than 0.99, X+y=1 and be such: when (1) characterized when the X-ray spectrogram by the table III, " y " less than 0.9615, " X " was greater than 0.0385; (2) when the X-ray spectrogram by the table VII characterized, " X " and " y " was all greater than 0.01, less than 0.99; Or (3) " y " be greater than 0.7776, and less than 0.9615 or less than 0.05, " X " is greater than 0.0385, less than 0.2224 with greater than 0.5.

Terminology used here " unit empirical formula " is represented the simplest formula according to its common implication.This simplest formula has provided the relevant mole number of titanium and silicon, and these titaniums and silicon form the TiO of titanosilicate molecular sieve of the present invention ₂And SiO ₂Tetrahedron element, and the framework of molecular sieve of formation TiSO composition.The unit empirical formula that provides according to titanium, silicon and oxygen is shown in following formula (1), it does not comprise other compound, positively charged ion or negatively charged ion, and these compounds, positively charged ion formula negatively charged ion may be other impurity or the materials that is produced by preparation or exist in not containing the integrally combined thing of above-mentioned tetrahedron element.When providing class synthetic unit empirical formula, it is reported that a certain amount of organic formwork agent R is as the part of composition, and water also may be as the part of composition, unless be defined as anhydrous form.For convenience's sake, the coefficient of organic formwork agent " R " " m " note is done such value, this value is defined as the total mole number of the mole number of organic formwork agent divided by titanium and silicon.

Unit empirical formula to a given TiSO can calculate with the chemical analysis data of TiSO.Therefore, the preparation TiSO that is for example introduced hereinafter _sIn, the composition of all class synthetic TiSO all calculates with chemical analysis data, and represents (representing with moisture-free basis) with mole oxide compound ratio.

Can on " class synthetic " basis, provide the unit empirical formula to TiSO, perhaps can carry out certain last handling process (as roasting) and provide the unit empirical formula afterwards at " class synthetic " TiSO composition.When the value of " m " is that 0.01-is about 0.3 the time, a group TiSO composition of formula (1) is better.The term here " class synthetic " carries out aftertreatment at the TiSO composition and carries out the formed TiSO composition of hydrothermal crystallization before removing wherein any evaporable component that exists singly relating to.TiSO to aftertreatment, the actual value of " m " will depend on Several Factors (comprising: special TiSO, template, according to the severity of the aftertreatment of the ability of from TiSO, removing template, recommend TiSO composition that uses or the like), the value of " m " can be within the scope of the defined value of class synthetic TiSO composition, except in such last handling process template be added among the TiSO handle, " m " value is usually less than the value of class synthetic TiSO.Except " m " value usually less than about 0.02, and preferably less than outside 0.01, an empirical formula with formula (1) expression is usually arranged with the TiSO composition of roasting or other aftertreatment forms.

Be enough under the harsh post-treatment condition, high-temperature roasting long period (above 1 hour) in air for example, " m " value can be zero or the sort of situation no matter, and template R can not be found by the analytical procedure of routine.

TiSO molecular sieve of the present invention usually be contain active titanium source, silicon, oxygen and preferably the reaction mixture of one or more organic formwork agents carry out hydrothermal crystallization and synthetic.Optional basic metal may reside in the reaction mixture.Reaction mixture usually is to be placed in the pressurized vessel, preferably make lining (as tetrafluoroethylene) with inert plastic, and heating, preferably under spontaneous pressure, in about 50 ℃-about 250 ℃ significant temp scope, up to obtaining the crystalline molecular sieve product.Usually working lipe when several to several weeks, about 2 hours of working lipe to about two weeks typically.Yet synthetic molecular sieve of the present invention is not need so for a long time, finds to introduce reaction mixture at general stirring or other appropriate stirred reaction mixtures and/or the TiSO crystal seed that will produce or a kind of topology ground analogous composition, to promote crystallisation process.Can reclaim product with any ordinary method (as centrifugation or filtration).

After the crystallization, the TiSO that can emanate out, then the washing and at air drying.The result of hydrothermal crystallization, class synthetic TiSO usually are included in the crystallization of its template of used at least a form in forming in the pore system.Usually, template is an organic molecular species type, if allow to consider from space angle, to exist with the positively charged ion of charge balance be possible to certain template at least.Usually template is too big, so that can not freely move through the interior pore system of the crystal of formed TiSO, and can remove by last handling process, for example at about 200 ℃-Yue 700 ℃ roasting temperature TiSO, so that the thermolysis template, or with certain other last handling process removes out template to small part from TiSO.In some cases, the hole of TiSO is sufficiently big, to such an extent as to allow the migration of template, therefore, with the method (for example using the zeolite desorption) of the desorption of routine can be all or part of remove template.

The TiSO composition is preferably by containing active TiO ₂Source and SiO ₂The reaction mixture of source and a kind of organic formwork agent forms, and above-mentioned reaction mixture contains a kind of composition of representing with mole oxide compound ratio:

aR ₂O∶（Ti _xSi _y）O ₂∶bH ₂O

R is a kind of organic formwork agent in the formula, and " a " is the significant quantity that forms " R " of above-mentioned TiSO composition, better is greater than zero to about 50, is more preferably about 0.5-10; " b " is the significant quantity of water, its value is zero-and Yue 400, better be 50-100 approximately; " X " and " y " represents at (Ti respectively _xSi _y) O ₂The molar fraction of titanium and silicon in the constituent, and one at least 0.001 value is all arranged separately, better be at least 0.01.

Form these TiSO _SThe reaction mixture of composition usually contains one or more organic formwork agents (template), and these template are those template that are used for synthetic aluminosilicate and aluminate or phosphate of mentioning in the past mostly.Template preferably contains VA family element, particularly nitrogen, phosphorus, arsenic and/or the antimony at least a periodictable, better is nitrogen or phosphorus, nitrogen preferably, and formula R is arranged ₄X ⁺, X chooses a group of being made up of nitrogen, phosphorus, arsenic and/or antimony in the formula; R is hydrogen, alkyl, aryl, aralkyl or alkaryl, and aryl or contain the alkyl of 1-8 carbon atom preferably, but may reside in " R " gene of template greater than the alkyl of 8 carbon atoms.Nitrogenous template is best, and it includes glue and quaternary ammonium compound, and the latter usually is by formula R ₄' N ⁺Expression, each R ' is alkyl, aryl, alkaryl formula aralkyl in the formula; As mentioned above, when R ' was alkyl, R ' preferably contained 1-8 carbon atom or more carbon atoms, and when R ' was other bases, R ' preferably contained more than 6 carbon atoms.The polymeric quaternary ammonium salt is as ((C ₁₄H ₃₂N ₂) (OH) ₂) _xX has an also value of available at least 2 in the formula.One, two and triamine, comprise that mixed amine also can be used as template, perhaps usefulness separately, perhaps with quaternary ammonium compound, quaternary phosphonium compound or other template are mixed and are used.When template was share, the definite relation between the various template was not really understood.Two or more template mixtures can be produced or TiSO _sMixture perhaps has such example, and wherein a kind of template is stronger than other template control action kou, the stronger template of control action kou can with other the process of template control hydrothermal crystallization of PH condition that is used for setting up reaction mixture at first.Representational template comprises: tetramethyl-ammonium, and tetraethyl ammonium, tetrapropyl ammonium, the TBuA ion, two-just-propyl ammonium, tripropylamine, triethylamine, trolamine,

Pyridine, cyclo-hexylamine, 2-picoline, N, N-dimethyl benzylamine, N, the N-ethylethanolamine, dicyclohexylamine, N, N-dimethylethanolamine, 1,4-diazabicylo (2.2.2) octane, N methyldiethanol amine, N-methyl-thanomin, N-methylcyclohexyl amine, 3-methyl-pyridine, the 4-picoline, rubane, N, N '-dimethyl-1,4-diazabicylo (2.2.2) octane ion, two-just-butylamine, neo-pentyl amine, two-n-pentyl amine, isopropylamine ,-butylamine, 1,2-quadrol, tetramethyleneimine and 2-imidazolone.For the people who is skilled in technique, all very clear, though single kind of template, under the reaction conditions of suitably selecting, can be used for producing multi-form TiSO composition, and available different template is produced given TiSO composition, but is not that each template all will produce each TiSO composition.

At alkoxide is in those examples in active titanium and/or silicon source, must have corresponding alcohol in reaction mixture, because alcohol is the hydrolysate of alkoxide.So far can't determine that whether this alcohol participate in the synthetic process as template or participate in other effect, though it can be used as template,, do not report that it is at TiSO _sIn modular as a kind of template.

When there is alkali metal cation in reaction mixture, it can promote certain TiSO _sCrystallization, if any, the definite effect of these positively charged ions in crystallisation process also do not known now.Be present in the TiSO composition that alkali metal cation in the reaction mixture generally appears at formation, perhaps as (adding) positively charged ion that is mingled with and/or as the structural cation of the net negative charge at various positions in the balance lattice.Though should be understood that to TiSO _sThe modular existence of not narrating alkali metal cation especially, but these alkali metal cations are with the hydrogen cation that provides especially in the general formula of zeolite aluminosilicate and/or the meaning difference of hydroxyl.

Here most active titanium source can be used.Reasonable active titanium source comprises the titanium alkoxide, water-soluble titanate, titanium chelate, titanium alcohol ester and titanium salt or the like.

Here most activated silica source can be used.Reasonable activated silica source is a silicon-dioxide, itself or silicon sol or the silicon-dioxide of smoking, the unbodied sedimentary silicon-dioxide of active solid, silica gel, the alkoxide of silicon, silicic acid or alkalimetal silicate and their mixture.

The every other X-ray spectrogram of resulting here X-ray spectrogram and appearance or obtain with the X-ray powder diffractive technology of (1) standard; (2) obtain with computer with copper K-α radiation, this computer based is in using Siemens D-500 X-ray powder diffractometer technology, Siemens type K-805 X-ray source, suitable computer interface, its can by newly translate Xi Zhou, Cherry Hill Siemens company obtains.When with the Standard X-Ray technology, radioactive source is a kind of high strength copper target, and the X-x ray tube is in 50KV and 40ma operation.Spectrogram by copper K-α radiation and graphite monochromator can suitably be used X-x ray spectrometer x scintillometer, pulse efficient analysis instrument and strip chart recorder record.The powder sample that flattens with two seconds time constants, scans at 2 ° of per minutes (2 θ).Obtain interplanar distance (d) with dust (A °) unit by the position of the diffraction peak of representing in 2 θ, its θ is observed cloth loudspeaker lattice (Bragg) angle on strip chart.Intensity is that the height from diffraction peak records after removing background." Io " is the intensity at the strongest peak, and " I " is the intensity at each other peak.When reporting relevant intensity here, the meaning of following abbreviation is: VS=is very strong; S=is strong; M=is medium; A little less than the W=; VW=is very weak.Other abbreviation comprises: the sh=shoulder; Br=is wide.

Can know all that for the people who is skilled in technique the mensuration of 2 θ parameters has people and equipment error, it combines, and can influence approximately ± 0.4 ° uncertain value 2 θ values of each report.Certainly, this uncertain value also shows the d-interplanar distance value of reporting for work, and d-interplanar distance value is calculated by 2 θ values.This out of true situation is general runs through whole technological process, and is not enough to get rid of crystallized stock of the present invention each other with the difference between the composition of former Technology.

Provided embodiment below situation of the present invention has been described, still, in any case these embodiment also do not mean that restriction the present invention.

Embodiment 1-18

(a) embodiment 1-18 is an explanation TiSO preparation of compositions method of the present invention.These TiSO compositions obtain by hydrothermal crystallization methods discussed above.Concerning each embodiment, reaction mixture all is to be equipped with one or more reagent of preparing below:

(a) Tipro: titanium isopropylate;

(b) 30(of LUDOX-LS:Dupont trade mark is heavy) %SiO ₂Heavy with 0.1() %Na ₂The low soda water solution of O;

(c) 40(of LUDOX-AS:Dupont trade mark is heavy) %SiO ₂Heavy with 0.08() %Na ₂The titanium stabilized aqueous solution of O;

(d) ammonium hydroxide;

(e) sodium hydroxide;

(f) TBAOH: TBAH;

(g) TEAOH: tetraethyl ammonium hydroxide;

(h) TPAOH: TPAOH;

The method that component above-mentioned is added in the reaction mixture is to carry out according to three kinds of methods (A, B and C).Method A, B and C are as follows:

Method A

LUDOX-LS and 1/3 water mix and form a kind of uniform mixture.Dissolution of sodium hydroxide in 2/3 water, and is mixed with said mixture, form a kind of uniform mixture.Titanium isopropylate is mixed in this mixture, then added organic template (TPAOH).Concoct this mixture then up to forming uniform mixture.

Method B

The method category-B is similar to method A, and only LUDOX-LS mixes with 80% water, and sodium hydroxide mixes with 20% water.

Method C

LUDOX-AS ammonium hydroxide and water are mixed, form a kind of uniform mixture.Titanium isopropylate is added in this mixture, and is admixed to the uniform mixture of formation.Add TBAH, this mixture of fusion again is up to forming uniform mixture.

(b) table 1 has been listed the preparation result of TiSO-45 and TiSO-48, and wherein all ingredients is represented by following mole number respectively:

CR∶dTiO ₂∶eSiO ₂∶fNaoH∶gH ₂O

C in the formula, d, e, f and g represent organic formwork agent R, TiO respectively ₂, SiO ₂, NaOH and H ₂The mole number of O.

Embodiment 19

Resulting TiSO-45 product in 600 ℃ of roastings one hour, is measured its adsorptive power among the embodiment 10 in air.This adsorptive power is used under the vacuum and measures in 350 ℃ of activatory samples with Mike Bake (MCBain-BaKr) the weight absorption instrument of standard.The data of the TiSO-45 that records are as follows:

(example 10) TiSO-45

Kinetic diameter pressure and temp adsorptive capacity

A ° mmHg ℃ heavy %

O ₂3.46 105 -183 11.8

O ₂3.46 741 -183 13.4

Hexanaphthene 6.0 65 23.6 2.5

Neopentane 6.2 739 23.5 1.3

H ₂O 2.65 4.6 23.8 2.7

H ₂O 2.65 20 24.0 6.1

The TiSO-45 of the above-mentioned roasting of a part measures adsorptive power with the chlorohydric acid pickling of 1N, and data are as follows:

Kinetic diameter pressure and temp adsorptive capacity

A ° mmHg ℃ heavy %

O ₂3.46 105 -183 14.1

O ₂3.46 741 -183 15.8

Hexanaphthene 6.0 65 23.6 3.0

Neopentane 6.2 739 23.5 1.4

H ₂O 2.65 4.6 23.8 2.8

H ₂O 2.65 20 24.0 6.6

Embodiment 20

(a) the class synthetic product of analysis (chemical analysis) example 10 and example 18 is measured because the SiO of molded existence ₂, Na ₂O, TiO ₂, the LOI(ignition loss), the weight percentage of carbon (c) and nitrogen (N).Analytical results is as follows:

(b) (example 10) TiSO-45

Component weight percentage

SiO ₂68.3

TiO ₂13.7

Na ₂O 3.7

C????5.8

N????0.6

LOT????12.5

Above chemical analysis obtains an anhydrous chemical formula:

0.040R（Si _0.869Ti _0.132）

(c) (example 18) TiSO-48

Component weight percentage

SiO ₂82.8

TiO ₂3.8

Na ₂O 0.05 ^★

C????7.3

N????0.71

LOI????13.2

★ is less than 0.05

Above chemical analysis obtains an anhydrous chemical formula

0.038R（Si _0.967Ti _0.033）

(c) to be the prepared TiSO product of use-case 10 carry out on the crystal of cleaning (with the diamond powder polishing and cover carbon) in microprobe analysis EDAX(energy-dispersive X-ray analysis).The EDAX microscopic analysis has shown the existence of titanium such as the crystalline particle of same whole part of TiSO composition.SiO ₂, TiO ₂And Na ₂The relative populations of O is expressed as follows by weight percent:

The table I

Point is visited and is analyzed

（Spot????Prcb）

Ti????3.4

Si????10.0

Ae????1.2

Embodiment 21

A) TiSO-45 that can prepare in example 10 carries out x-ray analysis.TiSO-45 is determined to be had a distinctive powdery diffractometry spectrogram other contains the d-spacing, expression in following table 11:

The table II

2θ d（A°） I/I _O×100

5.8 ^★15.24 23

6.5 ^★13.39 16

7.3 ^★12.11 23

7.8????11.33????43

8.2????10.78????18

8.7????10.16????32

9.5 ^★9.31 18

11.8????7.50????11

12.3 ^★7.20 7

Table II (continuing)

2θ????d（A°）????I/IO×100

13.1????6.76????7

13.8????6.42????7

14.5????6.11????11

15.1 ^★5.87 7

15.4????5.75????7

15.8????5.61????7

16.2????5.47????7

17.2????5.16????7

17.6????5.04????7

19.1????4.65????7

20.2????4.40????11

20.7????4.29????11

21.6????4.11????11

22.1????4.02????14

23.0????3.87????100

23.2????3.83????64

23.6????3.77????36

23.8????3.74????43

24.3????3.66????29

24.8????3.59????11

25.4????3.507????14

25.8????3.453????18

26.5????3.363????18

26.8????3.326????18

Table II (continuing)

2θ????d（A°）????I/IO×100

27.4????3.255????11

28.0????3.187????11

28.3????3.153????11

29.2????3.058????14

29.8????2.998????18

30.2????2.959????11

31.1????2.876????7

32.0????2.797????7

32.7????2.739????7

34.3????2.614????11

35.6????2.522????7

35.9????2.501????11

37.4????2.404????7

45.0????2.014????11

45.2????2.006????11

46.3????1.901????7

47.4????1.918????7

48.1????1.892????7

48.4????1.881????7

51.5????1.774????7

54.8????1.675????7

^★The impurity peak value

(b) the synthetic TiSO-45 composition of all classes that has obtained X-ray powder diffraction data so far has the spectrogram that is characterised in that following III data:

The table III

2 θ d(A °) relative intensity

7.8-8.0????11.33-11.05????m-vs

8.7-8.9????10.16-9.95????W-vs

23.0-23.1????3.87-3.85????m-vs

23.2-23.3????3.83-3.82????m

23.8-24.0????3.74-3.71????m

(c) partly (a) goes on foot class synthetic TiSO-45, in air, 600 ℃ of roastings one hour.The X-ray powder diffraction spectrogram of table IV below the product of roasting is characterised in that:

The table IV

2θ????d（A°）????100×1/10

7.9????11.19????100

8.9????9.94????83

9.1????9.72????25

9.9????8.93????8

13.3????6.66????13

13.9????6.37????17

14.8????5.99????21

15.6????5.68????17

16.0????5.54????17

16.6????5.34????8

17.8????4.98????13

18.3????4.85????8

19.3????4.60????8

20.4????4.35????13

Table IV (continuing)

2θ????d（A°）????100×1/10

20.9????4.25????7

21.8????4.08????17

22.2????4.00????13

23.1????3.85????83

23.3????3.82????58

23.7????3.75????38

23.9????3.72????38

24.4????3.65????29

25.6????3.480????13

25.9????3.444????17

26.6????3.351????21

26.9????3.314????17

28.4????3.143????13

29.3????3.048????17

29.9????2.988????21

30.2????2.959????17

30.4????2.940????13

31.3????2.858????13

32.2????2.780????8

32.8????2.730????13

34.4????2.607????13

36.1????2.488????13

37.6????2.392????13

45.1????2.010????17

Table IV (continuing)

2θ????d（A°）????100×1/10

45.5????1.994????17

47.5????1.914????13

(d) obtained so far the X-ray powder spread out the TiSO-45 composition of data have it is characterized in that below the X-ray powder diffraction shown in the table V:

The table V

2θ????d（A°）????100×1/10

7.8-8.0????11.33-11.05????23-100

8.7-8.9????10.16-9.94????16-99

9.1-9.2????9.72-9.61????14-25

11.8-12.0????7.50-7.38????2-11

13.1-13.3????6.76-6.66????6-7

13.8-14.0????6.42-6.33????7-11

14.5-14.8????6.11-5.99????11-15

15.4-15.6????5.75-5.68????7-8

15.8-16.0????5.61-5.54????7-10

16.2-16.6????5.47-5.34????2-7

17.2-17.9????5.16-4.96????5-9

19.1-19.3????4.65-4.60????3-7

20.2-20.4????4.40-4.35????4-11

20.7-20.9????4.29-4.25????9-11

21.6-21.8????4.11-4.08????3-11

22.1-22.2????4.02-4.00????3-4

23.0-23.1????3.87-3.85????50-100

Table V (continuing)

2θ????d（A°）????100×1/10

23.2-23.3????3.38-3.82????36-64

23.6-23.8????3.77-3.74????18-36

23.8-24.0????3.74-3.71????24-43

24.3-24.8????3.66-3.59????2-29

25.4-25.7????3.507-3.466????2-14

25.8-26.3????3.543-3.389????5-18

26.3-26.7????3.389-3.339????2-18

26.9-27.0????3.314-3.302????6-7

27.4-27.5????3.255-3.243????2-11

28.0-28.2????3.187-3.164????1-11

28.3-28.5????3.153-3.132????2-11

29.2-29.3????3.058-3.048????5-14

29.8-30.0????2.998-2.979????7-18

30.2-30.4????2.959-2.940????4-11

31.1-31.3????2.876-2.858????2-7

32.0-32.1????2.797-2.788????5-7

32.7-32.8????2.739-2.730????2-7

34.3-34.4????2.614-2.607????2-11

34.7-35.0????2.585-2.564????1-2

35.6-35.8????2.522-2.508????2-7

35.9-36.1????2.501-2.488????4-11

37.3-37.6????2.411-2.392????2-7

45.0-45.1????2.014-2.010????6-11

45.2-45.6????2.006-1.989????7-11

Table V (continuing)

2θ????d（A°）????100×1/10

46.3-46.7????1.901-1.945????2-7

47.4-47.5????1.918-1.914????2-7

48.0-48.1????1.895-1.892????6-7

48.4-48.8????1.881-1.866????2-7

51.5-51.9????1.774-1.762????1-7

54.8-55.0????1.675-1.670????2-7

55.2????1.664????1-2

Embodiment 22

(a) carry out x-ray analysis as the TiSO-45 for preparing in the example 18 and also measure, it has distinctive X-ray spectrogram, the d-spacing shown in the table VI below this spectrogram is included at least:

The table VI

2θ????d（A°）????100×1/10

7.9????11.13????55

8.8????10.00????37

11.9????7.44????6

12.4????7.12????3

13.2????6.70????3

13.8????6.41????2

13.9????6.37????2

14.7????6.05????5

14.8????5.99????6

15.9????5.57????5

Table VI (continuing)

2θ????d（A°）????100×1/10

17.7????5.00????3

19.3????4.60????5

20.3????4.37????10

20.7????4.29????2

20.8????4.26????3

22.3????3.99????3

23.1????3.84????100

23.9????3.72????44

24.3????3.66????13

25.6????3.479????3

26.7????3.341????5

26.9????3.319????4

29.3????3.048????7

29.9????2.986????10

34.3????2.614????3

35.1????2.554????2

35.7????2.515????2

36.1????2.491????5

37.4????2.403????2

45.1????2.010????9

46.1????1.968????2

47.3????1.901????2

48.5????1.876????4

54.7????1.680????2

55.0????1.669????3

(b) all TiSO-48 compositions that obtained X-ray powder diffraction data so far have it is characterized in that below the data of table VII:

The table VII

2 θ d(A °) relative intensity

7.9-8.0????11.13-11.12????m-vs

8.8????10.00????m

14.7-14.8????6.05-5.97????vw-w

23.1-23.2????3.84-3.83????m-vs

23.9-24.0????3.72-3.71????m

(c) partly (a) goes on foot class synthetic TiSO-48, and at 500 ℃, roasting is 1.5 hours in air, the X-ray powder diffraction spectrogram of table VIII below the product of roasting is characterised in that:

The table VIII

2 θ d(A °) relative intensity

8.0????11.12????100

8.8????10.00????58

11.9????7.44????1

13.3????6.68????5

14.0????6.35????2

14.8????5.97????14

15.5????5.71????2

15.9????5.57????8

17.7????5.00????5

19.3????4.60????3

20.4????4.35????5

20.8????4.27????2

Table VIII (continuing)

2 θ (A °) relative intensity

23.2????3.83????49

23.7????3.75????7

24.0????3.71????22

24.4????3.65????6

25.6????3.479????3

26.3????3.389????1

26.8????3.326????3

29.3????3.048????4

30.0????2.976????7

31????2.858????1

34.5????2.603????2

35.8????2.511????2

36.1????2.491????3

37.3????2.408????1

37.6????2.395????2

45.2????2.006????4

45.4????1.998????4

48.7????1.869????2

55.1????1.668????2

55.2????1.663????2

(d) the TiSO-48 composition that has obtained X-ray powder diffraction data so far have it is characterized in that below represented X-ray powder diffraction spectrogram in the table IX:

The table IX

2θ????d（A°）????100×1/10

7.9-8.0????11.13-11.12????55-100

8.8????10.00????37-58

11.9????7.44????1-6

12.4????7.12????3

13.2-13.3????6.70-6.68????3-5

13.8????6.41????2

13.9-14.0????6.37-6.35????2

14.7-14.8????6.05-5.97????5-14

15.5????5.71????2

15.9????5.57????5-8

17.7????5.00????3-5

19.3????4.60????3-5

20.3-20.4????4.37-4.35????5-10

20.7-20.8????4.29-4.27????2-3

22.3????3.99????3

23.1-23.2????3.84-3.83????49-100

23.7????3.75????7

23.9-24.0????3.72-3.71????22-44

24.3-24.44????3.66-3.65????6-13

25.6????3.479????3

26.3????3.389????1

26.7????3.341????5

26.8-26.9????3.326-3.319????3-4

29.3????3.048????4-7

Table IX (continuing)

2θ????d（A°）????100×1/10

29.9-30.0????2.986-2.976????7-10

31.3????2.858????1

34.3-34.5????2.614-2.603????2-3

35.1????2.554????2

35.7-35.8????2.515-2.511????2

36.1????2.491????3-5

37.3-37.4????2.408-24.03????1-2

37.6????2.395????2

45.1-45.2????2.010-2.006????4-9

45.4????1.998????4

46.1????1.968????2

47.3????1.901????2

48.5-48.7????1.876-1.869????2-4

54.7????1.680????2

55.0-55.1????1.668-1.669????2-3

55.2????1.663????2

Embodiment 23

In order to prove the catalytic activity of TiSO composition, will carry out pickling (1 equivalent hydrochloric acid) through the product sample in the example 10 after the roasting (in air, at 600 ℃, roasting 1 hour) and make FCC tests.The method of using is at the external diameter (O.D.) 1/2 that is equipped with approximately greater than the TiSO sample (20-40 order) of 5 gram tests " the 2%(mole that catalytic cracking is pre-mixed in nitrogen gas stream in the quartz tube reactor) normal butane.Sample is on the spot at 500 ℃, at 200cm ³The helium flow velocity of/minute purification activates 60 minutes down.Then, the 2%(mole in helium) normal butane is with 50cm ³/ minute flow velocity on test sample by 40 minutes, every 10 minutes analysed preparations, count standard one-level velocity constant then, in the hope of the catalytic activity of TiSO composition, the K of resulting TiSO composition _AValue (cm ³/ gmin) be expressed as follows:

Sample embodiment velocity constant K _A

10????0.3

10 ^★0.3

^★The pickling sample.

Embodiment 24(comparative example)

This is a comparative example.Wherein, repeat the embodiment 1 of european patent application 82109451.3, and estimate this product by several technique means of following discussion:

(a) embodiment 1 of repetition european patent application 82109451.3, its initial reaction mixture have following composition (meter in molar ratio):

1Al ₂O ₃∶47SiO ₂∶1.32TiO ₂∶11.7NaOH∶28TPAOH∶1498H ₂O。This reaction mixture branch opens into two digestors.When the end of processing described in the example 1 of european patent application, analyze the sample of product in each steeping vat, draw following chemical analysis results:

Weight percentage

Sample 1 sample 2

SiO ₂75.3 75.9

Al ₂O ₃3.02 2.58

TiO ₂3.91 4.16

Na ₂O 3.66 3.46

Carbon 6.3 6.7

Nitrogen 0.62 0.65

The LOI(ignition loss) 14.0 14.0

Then, use the SEM(scanning electronic microscope) and EDAX(energy dispersion x-ray analysis) these two samples of microprobe analysis.The SEM test result of these two samples shows four kinds of forms of existence, as shown in Figure 1.

Four kinds of forms of these two kinds of samples can prepare according to european patent application, and every kind of form EDAX microprobe analysis result is as follows:

(1) level and smooth, symbiotic sexangle particle (B among Fig. 1), the form that it relates to ZSM-5 has following EDAX microprobe result:

Visit some mean number

Ti????0

Si????1.0

Al????0.05

(2) flat: level and smooth sheet (A among Fig. 1) has following EDAX microprobe result:

Visit some mean number

Ti????0.13

Si????1.0

Al????0.05

(3) spherical and extended rice (C among Fig. 1) has following EDAX microprobe result:

Visit some mean number

Ti????0.22

Si????1.0

Al????0.05

Na????0.10

(4) aciculiform or bar-shaped (D among Fig. 1) have following EDAX microprobe result:

Visit some mean number

Ti????0.05

Si????0.8

Al????0.13

Na????0.05

Cl????0.10

Generated the crystallization of ZSM-5 type though above-mentioned SEM and EDAX data show, these crystallizations do not contain detectable titanium.Detectable titanium only exists mutually as impurity, not in the crystal with ZSM-5 structure.

Also obtain the X-ray diffraction spectrogram of class synthetic.Observed X-ray spectrogram is as follows:

Table X (sample 1)

5.577????15.8467

5.950????14.8540

6.041????14.6293

6.535????13.5251

7.154????12.3567

7.895????11.1978

8.798????10.0504

9.028????9.7946

9.784????9.0401

11.846????7.4708

12.453????7.1079

12.725????6.9565

13.161????6.7267

Table X (sample 1) (continuing)

13.875????6.3821

14.637????6.0518

14.710????6.0219

15.461????5.7310

15.881????5.5802

16.471????5.3818

17.218????5.1498

17.695????5.0120

19.212????4.6198

19.898????4.4619

20.045????4.4295

20.288????4.3770

20.806????4.2692

21.681????4.0988

22.143????4.0145

23.091????3.8516

23.641????3.7632

23.879????3.7263

24.346????3.6559

24.649????3.6116

25.548????3.4865

25.828????3.4494

26.228????3.3976

26.608????3.3501

26.887????3.3158

Table X (sample 1) (continuing)

27.422????3.2524

28.048????3.1812

28.356????3.1473

29.191????3.0592

29.912????2.9870

30.295????2.9502

32.736????2.7356

33.362????2.6857

34.355????2.6102

34.640????2.5894

34.887????2.5716

35.152????2.5529

35.551????2.5252

35.660????2.5177

36.031????2.4926

37.193????2.4174

37.493????2.3987

45.066????2.0116

45.378????1.9985

46.514????1.9523

47.393????1.9182

Table XI (sample 2)

5.801????15.2353

6.012????14.7012

6.169????14.3265

7.970????11.0926

8.875????9.9636

9.118????9.6981

9.879????8.9532

11.933????7.4163

12.537????7.0605

12.808????6.9115

13.242????6.8680

13.957????6.3452

14.718????6.0186

14.810????5.9813

15.542????5.7014

15.954????5.5551

16.563????5.3521

17.316????5.1211

17.788????4.9862

19.291????4.6009

20.119????4.4134

20.382????4.3571

20.879????4.2544

21.735????4.0887

22.220????4.0007

Table XI (sample 2) (continuing)

23.170????3.8387

23.730????3.7494

23.964????3.7133

24.425????3.6442

24.722????3.6011

25.900????3.4399

26.734????3.3345

26.979????3.3047

27.251????3.2724

27.494????3.2440

28.175????3.1671

28.450????3.1371

29.287????3.0493

29.970????2.9814

30.371????2.9430

30.694????2.9127

31.312????2.8566

32.825????2.7283

33.457????2.6782

34.426????2.6051

34.723????2.5834

34.879????2.5722

35.709????2.5143

36.125????2.4863

37.248????2.4139

Table XI (sample 2) (continuing)

37.490????2.3988

45.156????2.0078

45.453????1.9954

46.462????1.9544

46.608????1.9486

Table X and XI have shown the figure of the distinctive X-ray of ZSM-5 type product, and can think not contain the figure that the level and smooth symbiosis sexangle particle of titanium is become.The X-ray figure of table X and XI has demonstrated three peaks (2 θ=5.6-5.8,12.45-12.54 and 24.5-24.72), and this phenomenon can not be explained.Two samples are with in air, in calcining together through the various piece of each sample after the calcining in 16 hours under 540 ℃.This calcination condition is consistent with employed condition in European application No.82109451.3.The X-ray figure of this calcination product is as follows:

Table XII (sample 1)

6.141????14.3908

6.255????14.1303

8.011????11.0355

8.913????9.9209

9.144????9.6705

9.930????8.9068

11.979????7.3876

12.440????7.1152

13.289????6.6625

14.007????6.3224

14.874????5.9557

Table XII (sample 1) (continuing)

15.613????5.6757

15.995????5.5408

16.609????5.3373

17.353????5.1103

17.884????4.9597

19.335????4.5905

20.177????4.4008

20.463????4.3401

20.940????4.2422

21.845????4.0685

22.291????3.9880

23.186????3.8361

23.362????3.8076

23.817????3.7359

24.031????3.7031

24.510????3.6317

24.908????3.5747

25.699????3.4664

25.969????3.4309

26.371????3.3796

26.698????3.3389

27.022????3.2996

27.487????3.2449

28.184????3.1662

28.513????3.1303

Table XII (sample 1) (continuing)

29.369????3.0411

30.017????2.9769

30.468????2.9338

31.333????2.8548

32.877????2.7241

34.490????2.6003

35.062????2.5592

35.800????2.5082

36.186????2.4823

37.324????2.4092

37.654????2.3888

45.195????2.0062

45.631????1.9880

46.639????1.9474

47.547????1.9123

48.765????1.8674

Table VIII (sample 2)

6.092????14.5084

6.295????14.0403

7.941????11.1328

8.838????10.0054

9.857????8.9730

11.921????7.4236

12.399????7.1383

Table VIII (sample 2) (continuing)

13.222????6.6959

13.937????6.3539

14.811????5.9809

15.535????5.7038

15.916????5.5681

16.532????5.3620

17.262????5.1370

17.806????4.9811

19.268????4.6064

20.107????4.4160

20.389????4.3556

20.868????4.2567

21.807????4.0754

22.197????4.0047

23.116????3.8476

23.263????3.8235

23.755????3.7455

23.955????3.7147

24.432????3.6433

24.854????3.5823

25.653????3.4725

25.901????3.4398

26.265????3.3929

26.648????3.3451

26.976????3.3052

Table X III (sample 2) (continuing)

27.386????3.2566

28.156????3.1692

28.495????3.1323

29.304????3.0476

29.969????2.9815

30.384????2.9417

31.283????2.8592

32.819????2.7289

34.423????2.6052

34.993????2.5641

35.716????2.5138

36.146????2.4850

37.295????2.4110

37.562????2.3944

45.137????2.0086

45.523????1.9925

46.562????1.9504

47.509????1.9137

It is to be divided into the figure that attitude only has the ZSM-5 type of technicality with former that the X-ray diffraction figure of calcining sample shows.When a part of calcining sample 1 and 2 is carried out chemical analysis (aggregate analysis), just obtain following result:

Weight percentage

Sample 1 sample 2

SiO ₂79.6 81.2

Al ₂O ₃3.5 2.9

Na ₂O 4.4 4.1

TiO ₂4.4 4.6

C????0.1????0.10

L _oI 8.1 7.6

When top aggregate analysis result is calculated the mol ratio of its oxide compound, obtain following result:

1SiO ₂: 0.043TiO ₂: 0.021Al ₂O ₃: 0.049Na ₂The described a large amount of chemical analysis results of this result of O and European application are quite approaching, and the analytical results of European application is:

1SiO ₂: 0.047TiO ₂: 0.023Al ₂O ₃: 0.051Na ₂Though the product crystal that O gives product ZSM-5 X ray graphic feature not titaniferous is undoubtedly, the aggregate analysis result of product proves that titanium is to exist as crystal impurity, and this crystal impurity does not have ZSM-5 X-ray graphic feature.

Using method

TiSO composition of the present invention has unique surface characteristic, and this makes them can be used as molecular sieve and is used as catalyzer or is used as in various centrifugations the support of the catalyst in the hydrocarbon conversion and the oxidizing fire process.The TiSO composition can be impregnated or with known many methods on the technology it be combined with catalytically-active metals, and can be used for, and for example preparation contains the catalyst composition of aluminium or silico-aluminate material.

Available TiSO composition separates each quasi-molecule in the mixture of the various molecules with opposed polarity degree or different motion diameter, its method is that mixture is contacted with the TiSO composition, the aperture of TiSO composition is big to a kind of molecule that can adsorb mixture at least, but be not whole various molecules, this absorption is based on that the various molecules that are adsorbed and/or their motion diameter carry out.When the TiSO composition was used in such sepn process, the TiSO composition was the part activatory at least, thus some kind molecular selectivity enter in the intercrystalline body opening system of composition.

Comprise with TiSO composition catalysis hydrocarbon conversion reactions: cracking, hydrocracking: the alkylation of aromatics type and different alkane type; Isomerization (comprising the diformazan isomerization); Polymerization is reformed, hydrogenation, and dehydrogenation, alkyl transforms, and takes off alkyl and hydration.

When the TiSO that contains catalyst component contained the hydrogenation promotor, such promotor can be a platinum, palladium, and tungsten, nickel or molybdenum, and can be used for the refining various petroleums that contain the heavy residue oil plant, but the raw material of ring-type raw material and other hydrocrackings.These raw materials can be in hydrocracking under the following condition: temperature range is between about 400 °F and about 825 °F, and the molar ratio range of used hydrogen and hydrocarbon is between about 2 and about 80, and pressure is at about 10 and 3500 pounds/inch ²Between, the liquid hourly space velocity rate is between about 0.1 and about 20.Between more about 1.0 and about 10.

The TiSO that contains catalyst combination also can use in reforming process, and hydrocarbon feed is contacting with catalyzer under the following condition in this process: temperature is between about 700 °F and 1000 °F, and hydrogen pressure is about 100 and about 500 pounds/inch ²Between, liquid hourly space velocity rate value about 0.1 and about 10 scopes between, the mol ratio of hydrogen and hydrocarbon about 1 and about 20 scopes between.Between more about 4 and about 12.

In addition, contain in this catalyzer of TiSO(of catalyzer and contain the hydrogenation promotor), also can be applicable in the hydroisomerization process, in this process, charging (as normal alkane) changes into saturated branched chain isomer.Hydroisomerization process is generally being carried out under the following condition: temperature is between about 200 °F and about 600 °F, and between more about 300 °F and about 550 °F, liquid hourly space velocity rate value is between about 0.2 and about 1.0.The general supply response device of hydrogen, in the hydrocarbon feed mixture, the mol ratio of hydrogen and charging is between about 1 and about 5.

Containing the TiSO that is similar to the component that is used in hydrocracking and hysomer also can use under the following condition: temperature is between about 650 °F and about 1000 °, between more about 850 °F and about 950 °F, align alkane hydroisomerization, usually carry out under low slightly pressure, its scope is about 15 and about 50 pounds/inch ²Between.The alkane charging is preferably for containing the normal alkane of carbonatoms in the C7-C20 scope.For fear of unwanted pair of reaction such as polymerized hydrocarbon and alkane cracking reaction, charging and the duration of contact of containing between the TiSO of catalyzer are generally relatively short.Liquid hourly space velocity rate value about 0.1 and about 10 scopes between, more suitable between about 1.0 and about 6.0.

The low alkali content (can not measure with present analysis process usually) of instantaneous (instant) TiSO composition is particularly suitable in the conversion reaction of alkyl aromatic compound them, is specially adapted in the catalysis disproportionation of toluene, dimethyl benzene, Three methyl Benzene, tetramethyl-benzene and similar compounds.Find that in such disproportionation process isomerization and transalkylation also can take place.To the TiSO that contains the catalyzer that is applicable to this process generally only contain the noble metal promoted agent of the 8th family or precious metal and the 6th pair of family's metal as: tungsten, copper and chromium use together, and the content of these promotors is preferably between about 3 and the about 5 weight % that account for the catalyst component total amount in this catalyst component.But, can there be the hydrogen that adds to exist at conversion zone, but be not necessarily to need the hydrogen that adds to exist, the reaction conditions of this conversion zone remains between temperature about 400 and about 750; Pressure is about 100 and about 2000 pounds/inch ²Between the scope, liquid hourly space velocity rate value about 0.1 and about 15 scopes between.

The TiSO that contains catalyzer can be used in the catalytic cracking process, and it can be used in preferably as gas oil, and heavy raw gasline is in the chargings such as deasphalting crude oil residue, to obtain our needed main products gasoline.Reaction temperature material condition generally about 850 and about 1100 °F between, liquid hourly space velocity rate value is between about 0.5 and about 10, pressure condition is about 0 and about 50 pounds/inch ²Between.

The TiSO that contains catalyzer can be used for the dehydrocyclization reaction, and the straight-chain paraffin raw material is used in this reaction, better with the normal paraffin that has more than 6 carbon atoms, to generate benzene, dimethylbenzene toluene and similar compounds.Carry out under the reaction conditions that the dehydrocyclization process is generally used in being similar to catalytic cracking.To such process, the base metal of the 8th pair of family such as the positively charged ion of cobalt and nickel use better with the TiSO composition.

The TiSO that contains catalyzer can be used for catalysis and take off hydrocarbon reaction, and in reaction, the side chain of alkane disconnects from virtue nuclear, and ring structure does not have hydrogenation basically under following reaction conditions.Higher temperature of reaction is about between 800 and about 1000 scopes, and the hydrogen pressure of appropriateness is about 300 and about 1000 pounds/inch ²Between, other reaction conditions is similar to above-mentioned catalytic hydrogenation cracking conditions.Be used for the catalytic dealkylation reaction the TiSO that contains catalyzer and above-mentioned be same type about the TiSO described in the catalytic dehydrogenation cyclization.The dealkylation of special expectation is reflected at and comprises that here the methyl bitter edible plant changes into the bitter edible plant and toluene and/or dimethylbenzene and changes into benzene.

The TiSO that contains catalyzer can be used for catalytic hydrofinishing, and wherein main purpose provides to organosulfur and/or nitrogen compound hydrogenation component selectivity, and does not influence simultaneous hydrocarbon molecules substantially.Use with the general reaction conditions described in the above-mentioned catalytic hydrocracking better for this purpose.Catalyzer equally has identical general aspects with catalyzer described in relevant dehydrocyclization process.Catalytic hydrofinishing is normally used into to be comprised: gasoline fraction; Kerosene; The rocket engine fuel cut; Diesel oil distillate; Light and heavy gasoil, deasphalted crude residue, and similar compounds.Charging can contain up to about the sulphur of 5% weight with up to about the nitrogen of 3% weight.

Though isomerization process is tended to need be than being used for the more slightly an acidic catalyst of reforming process, the TiSO that contains catalyzer can be used in the isomerization process, carries out isomerized condition and is similar to the condition described in the above-mentioned reforming reaction.Isomerisation of olefin carries out better under the condition between about 500 and about 900 of the temperature, and straight chain hydrocarbon; Naphthenic hydrocarbon, and alkylaromatic hydrocarbon is isomerization under temperature between 700 and about 1000.The isomerization reaction of special expectation just here comprising-heptane and/or just-octane changes into isoheptane, octane-iso, butane changes into Trimethylmethane, methylcyclopentane changes into hexanaphthene, between-dimethylbenzene and/or ortho-xylene change into right-dimethylbenzene, 1-butylene changes into 2-butylene and/or iso-butylene, just-hexene changes into dissident's alkene, the hexamethylene hydrocarbon changes into reactions such as methylcyclopentane, the cationic form that takes a turn for the better is with the TiSO and second main group, polyvalent metal compounds (as the sulfide) combination of second pair of family's metal and rare earth metal.To alkylation with take off the alkyl process, the aperture that the TiSO composition has at least 5 dusts is good.When being used for the dealkylation of the fragrant hydrocarbon of alkyl, temperature is at least 350 °F usually, make charging basically the temperature range that takes place of cracking or conversion product reaction reach about 700 °F usually, temperature is at least 450 °F for good, and be not more than the critical temperature that compound carries out dealkylation, it is aqueous to keep aroamtic hydrocarbon raw material to be at least to pressurize.Alkylating temperature can be hanged down to 250 °F, but is at least 350 °F better.At benzene, in the alkylated reaction of toluene and dimethylbenzene, alkylating agent alkene is as ethene and propylene preferably.

TiSO composition of the present invention can be used in general molecule sieve in process, has used the molecular sieve of silico-aluminate, aluminophosphates or other common uses to carry out isolated molecule so far.The TiSO composition is before they are used for the molecular sieve technological process, and preferably activation earlier is to remove owing to synthetic or other reason are present in any molecule in the intercrystalline body opening system.To the TiSO composition, contain sometimes with adding organic compounds that heat collapse is present in a kind of former synthetic attitude TiSO and realize this activation, because so organic compounds may be too big so that can not make it remove absorption with general method.

TiSO composition of the present invention also can be used as sorbent material, and can separate each quasi-molecule, and above-mentioned two kinds of effects all are based on the property utmost point degree of molecular size (motion diameter) and each quasi-molecule.When the separation of each quasi-molecule is based on when selecting to adsorb according to molecular size, select TiSO according to the TiSO aperture, so that the infima species molecular energy of mixture enters intercrystalline body space at least, and the molecule of maximum kind can not enter at least.When separation was based on polarity degree, generalized case was that more hydrophilic TiSO has preferentially adsorbed this quasi-molecule of more polar in the mixture of opposed polarity degree, even two quasi-molecules can both combine with the hole system of TiSO.

Claims (24)

1, porous crystalline body titanium-silicate molecular sieve, the nominal diameter in its hole be greater than 3 dusts, and they become expression in the chemical ingredients of former synthetic attitude during with anhydrous form by following unit experience

Wherein " R " expression is present in the organic formwork agent in the system of intercrystalline hole; " m " represents every mole of (Ti _xSi _y) O ₂In the mole number of " R ", its value from zero to about 0.3; The value of " x " and " y " is generally greater than 0.01 and less than 0.99, x+y=1, and be such: when (1) comes representation feature when the X-ray figure with the table III, " y " less than 0.9615 " x " greater than 0.0385; (2) when using the X-ray figure representation feature of table VII, " x " and " y " is all greater than 0.01 and less than 0.99; Or (3) " y " is greater than 0.7776 with less than 0.9615 or less than 0.05; " x " is greater than 0.0385 with less than 0.2224 with greater than 0.5.

2, according to the molecular sieve of claim 1, wherein " X " and " y " is with (1) of claim 1

3, according to the molecular sieve of claim 2, wherein " X " and " y " is with (2) of claim 1

4, xln titanium-silicate molecular sieve, wherein " X " and " y " is with (3) of claim 1.

5, the titanium-silicate of claim 1 have list in table in the III with the X-ray powder diffraction pattern shape of levying.

6, the titanium-silicate of claim 1 has the X-ray powder diffraction pattern shape of listing in the feature in the table VII.

7, the titanium-silicate of claim 1 or claim 2, wherein " m " value is greater than 0.01 to 0.3.

8, the xln molecular sieve of claim 1 or claim 4, wherein said molecular sieve is through calcining to remove some organic formwork agents that exist at least.

9, the method for preparing xln titanium-silicate molecular sieve comprises: in efficient temperature with under with the effective time, provide a kind of reaction mixture components, be expressed as follows according to oxide mol ratio:

Wherein " R " is organic formwork agent: " a " is " R " significant quantity from greater than 0 to about 50; " b " value is for from 0 to about 400; At (Ti _xSi _y) in the part " X " and " y " represent the molar ratio of titanium and silicon respectively, and each value all is at least 0.01, thereby prepares the xln molecular sieve of claim 1 or claim 2.

10, according to the method for claim 9, wherein the source of silicon is a silicon-dioxide in the reaction mixture.

11, according to the method for claim 9, wherein titanium is from by pure titanium salt, and the water-soluble titanium hydrochlorate is selected in one group of compound that titanium chelate and titanic acid ester constitute to get.

12, according to the method for claim 8, wherein organic formwork agent is selected to get from being made of one group of compound following formula quaternary ammonium compound or quaternary phosphonium compound:

R ₄X ⁺

Wherein X is nitrogen or phosphorus, and each R contains at 1 alkyl or aryl to about 8 carbon atoms.

13, according to the method for claim 9, wherein template is selected from following one group of compound: the tetrapropyl ammonium ion; The tetraethyl ammonium ion; Tripropylamine; Triethylamine, trolamine;

Pyridine; Hexahydroaniline; The 2-picoline, N, N-dimethyl benzene methylamine, N, N-diethylethanolamine; Dicyclohexyl amine; N, the N-Dimethylethanolamine; Choline, N, the N-dimethyl, Piperazine, tetramethyleneimine; 1,4-diazabicyclo-(2,2,2) octane; The N-methyl

Pyridine; The 3-methyl Pyridine; N-methylcyclohexylamine; The 3-picoline; The 4-picoline; Rubane; N, N-dimethyl-1,4-diazabicyclo (2,2,2) octane ion; Tetramethyl ammonium; The TBuA ion; The four pentyl ammonium ion; Two-just-butylamine, neo-pentyl amine; Neo-pentyl amine; Two-just-amylamine; Isopropylamine; And polymeric quaternary ammonium salts ((C ₁₄H ₃₂N ₂) (OH) ₂) _xWherein the value of X is at least 2.

The method of 14, separating all kinds of molecule mixtures, wherein such mixture contain the various molecules with polarity in various degree and/or motion diameter, comprise that (or a kind of composition of claim 2 contacts with claim with said mixture.

15, transform the method for hydro carbons, be included under the hydrocarbon conversion condition, above-mentioned hydrocarbon is contacted with a kind of crystalline molecular sieve of listing in claim 1 or claim 2.

16, according to the method for claim 15, wherein hydroconversion process is cracking.

17, according to the method for claim 15, wherein hydroconversion process is hydrocracking.

18, according to the method for claim 15, wherein hydroconversion process is hydrogenation.

19, according to the method for claim 15, wherein hydroconversion process is polymerization.

20, according to the method for claim 15, wherein hydroconversion process is alkylation.

21, according to the method for claim 15, wherein hydroconversion process is heavy attitude.

22, according to the method for claim 15, wherein hydroconversion process is hydrofining.

23, according to the method for claim 15, wherein hydroconversion process is isomerization.

24, according to the method for claim 15, wherein hydroconversion process is a dehydrocyclization.