CN101514017B

CN101514017B - ZSM-5/mordenite/MCM-49 triphase coexisting molecular sieve and method for synthesizing same

Info

Publication number: CN101514017B
Application number: CN2008100431238A
Authority: CN
Inventors: 马广伟; 谢在库; 滕加伟; 肖景娴
Original assignee: China Petroleum and Chemical Corp; Sinopec Shanghai Research Institute of Petrochemical Technology
Current assignee: China Petroleum and Chemical Corp; Sinopec Shanghai Research Institute of Petrochemical Technology
Priority date: 2008-02-20
Filing date: 2008-02-20
Publication date: 2011-07-20
Anticipated expiration: 2028-02-20
Also published as: CN101514017A

Abstract

The present invention relates to a ZSM-5/mordenite/MCM-49 triphase coexisting molecular sieve and a method for synthesizing the same, and mainly solves the problems that a porous material synthesized by the prior art is single in pore-size, weak in acid and low in activity. The method prepares the ZSM-5/mordenite/MCM-49 triphase coexisting molecular sieve by adding a seed crystal containing an MCM-49 precursor during a synthesis process of ZSM-5/mordenite diphase coexisting molecular sieve. A mole relation of the components of the synthesized triphase coexisting molecular sieve is nSiO2: Al2O3, wherein n is between 10 and 1,000; the triphase coexisting molecular sieve has more than three phases; the XRD diffraction pattern of the triphase coexisting molecular sieve comprises a technical proposal that a maximum value of a distance d is at positions between 13.51-0.1 and 13.51+0.1 A, 12.26-0.2 and 12.26+0.2 A, 11.22-0.2 and 11.22+0.2 A, 9.97-0.1 and 9.97+0.1 A, 8.82-0.1 and 8.82+0.1 A, 7.74-0.1and 7.74+0.1 A, 6.14-0.1 and 6.14+0.1 A, 5.14-0.1 and 5.14+0.1 A, 4.15-0.1 and 4.15+0.1 A, 3.90-0.05 and 3.90+0.05 A, 3.71-0.1and 3.71+0.1 A, 3.45-0.05 and 3.45 +0.05 A, 3.20-0.05 and 3.20+0.05A, 3.08-0.04 and 3.08+0.04 A, and 2.98-0.05 and 2.98+0.05 A; therefore, the problems are solved well. The triphase coexisting molecular sieve can be used in the industrial production of ethylene and propylene through the catalytic pyrolysis of naphtha.

Description

ZSM-5/ mordenite/MCM-49 three-phase intergrowth molecular sieve and synthetic method thereof

Technical field

The present invention relates to a kind of ZSM-5/ mordenite/MCM-49 three-phase intergrowth molecular sieve and synthetic method thereof.

Background technology

Mordenite and ZSM-5 porous material are applied in field of petrochemical industry widely owing to have good shape selective catalysis performance and thermostability preferably.The aperture is evenly single separately, acidity is weak, activity is not high and selectivity is relatively poor, can not deal with complicated component separately, and they is to the catalytic performance difference of same reaction thing but owing to two kinds of molecular screen materials.Contain the above three-phase intergrowth molecular sieve of two kinds of components, contain multi-stage artery structure, strong acid weak acid distribution range is wider, can handle molecular diameter complex component not of uniform size, and can bring into play their concerted catalysis effect.

Document CN1565967A, CN1565970A report adopts mordenite or ZSM-5 as crystal seed, adds respectively in the resulting solution of ZSM-5 or mordenite, has synthesized the mixed crystal material of mordenite and ZSM-5.Its catalytic effect is better than the effect of two kinds of molecular sieve mechanically mixing, but needs to add different crystal seeds in the building-up process as inductor, also needs to add fluorochemical in addition, and building-up process is comparatively complicated.

Document CN1393403 report adopts the method for segmentation crystallization to synthesize middle mesoporous-microporous composite molecular sieve composition, is used for heavy oil upgrading.Synthetic method is to prepare the reaction mixture gel of synthetic microporous molecular sieve earlier, under 30～300 ℃ of conditions, carry out the crystallization of fs then, after the crystallization 3～300 hours, the pH value of adjusting reaction mixture is 9.5～12, and the synthetic used template of mesoporous molecular sieve of adding, and then at 30～170 ℃ from depressing the hydrothermal crystallizing that carries out subordinate phase, crystallization time is 15～480 hours, mesoporous-microporous composite molecular sieve composition in obtaining, but the building-up process of molecular sieve needs the segmentation crystallization, and the pH value also will be regulated in the centre, and synthetic method is also comparatively complicated.

Document CN03133557.8 has reported and has synthesized the composite structure molecular sieve with TON and two kinds of structures of MFI under the static conditions, this molecular sieve has added a spot of crystal seed and salt in the preparation gelation process, control suitable crystallization parameter, can obtain the molecular sieve of two kinds of crystal formation different ratioss, silica alumina ratio obtains the reaction process that composite molecular screen of the present invention can be used for mixture such as petroleum fractions greater than 50 on the lattice of molecular sieve.Building-up process of the present invention also needs to add crystal seed and salt.

Document CN1583562 has reported a kind of double-micropore zeolites molecular sieve and preparation method, it is characterized in that adopting orderly synthesis method, tentatively synthesizes y-type zeolite by certain material proportion earlier; After it is mixed with the tetraethyl-amine bromide solution that is dissolved with ammoniacal liquor, adding a certain amount of silicon sol at last more fully stirs and makes it even, in 130 ℃～140 ℃ following crystallization 4～7 days, obtain having the composite zeolite molecular sieve of the two microvoid structures of Y/ β, this method is also similar with the segmentation crystallization.

Summary of the invention

Technical problem to be solved by this invention one of is to be single, acid weak, the active not high problem of prior art synthetic aperture of porous material, and a kind of new ZSM-5/ mordenite/MCM-49 three-phase intergrowth molecular sieve is provided.This three-phase intergrowth molecular sieve has multi-stage artery structure, and strong acid weak acid distribution range is wider, active higher characteristics; Two of technical problem to be solved by this invention is the problems that do not relate to above-mentioned three-phase intergrowth molecular sieve preparation method in the prior art, and a kind of preparation method of new ZSM-5/ mordenite/MCM-49 three-phase intergrowth molecular sieve is provided.

For one of solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of ZSM-5/ mordenite/MCM-49 three-phase intergrowth molecular sieve, the composition with following molar relationship: nSiO ₂: Al ₂O ₃, n=10 in the formula～1000 is characterized in that described three-phase intergrowth molecular sieve has the thing phase more than three kinds, its XRD diffracting spectrum is included in 13.51 ± 0.1, and 12.26 ± 0.2,11.22 ± 0.2,9.97 ± 0.1,8.82 ± 0.1,7.74 ± 0.1,6.14 ± 0.1,5.14 ± 0.1,4.15 ± 0.1,3.90 ± 0.05,3.71 ± 0.1,3.45 ± 0.05,3.20 there is d-spacing maximum value at ± 0.05,3.08 ± 0.04,2.98 ± 0.05 dust places.

In the technique scheme, nSiO ₂: Al ₂O ₃The preferable range of n is n=20～400 in the formula, contains mordenite, three kinds of Symbionts of ZSM-5 and MCM-49 in the three-phase intergrowth molecular sieve at least mutually, and Symbiont phase adjustable ratio.

For solve the problems of the technologies described above two, the technical solution used in the present invention is as follows: the synthetic method of a kind of ZSM-5/ mordenite/MCM-49 three-phase intergrowth molecular sieve may further comprise the steps:

(1) silicon source, aluminium source, alkali source, template M and water are mixed, reaction mixture with molar ratio computing is: SiO ₂/ Al ₂O ₃=10～1000, OH ^-/ SiO ₂=0.001～10.0, M/SiO ₂=0.05～3.0, H ₂O/SiO ₂=10～500, be 8～14 with rare acid for adjusting pH value;

(2) SiO to contain in the silicon source ₂Weight is benchmark, adds an amount of crystal seed in above-mentioned mixing solutions, and amount of seed is SiO ₂0.01～20% of weight, crystal seed are SiO ₂/ Al ₂O ₃Mol ratio is 10～200 the crystal grain that contains the MCM-49 presoma amorphous substance in 1～500 nanometer;

(3) the above-mentioned reaction mixture that will mix is put into encloses container under autogenous pressure, 80～220 ℃ of crystallization 8～200 hours;

(4) crystallization is good product takes out, and washing is filtered, and after the drying, makes ZSM-5/ mordenite/MCM-49 three-phase intergrowth molecular sieve; Wherein used silicon source is to be selected from least a in organosilicon, soft silica, silicon sol, solid oxidation silicon, silica gel, diatomite or the water glass; Used aluminium source is at least a in the oxide compound of the oxyhydroxide that is selected from aluminate, meta-aluminate, aluminium salt, aluminium, aluminium or the aluminiferous mineral; Used alkali source is to be selected from least a in the alkali-metal oxyhydroxide; Template used dose of M is selected from least a in organic amine or the inorganic ammonium.

In the technique scheme, reaction mixture is with molar ratio computing, and preferable range is: SiO ₂/ Al ₂O ₃=20～400, OH ^-/ SiO ₂=0.01～5.0, M/SiO ₂=0.1～1.0, H ₂O/SiO ₂=20～300, crystal seed is SiO ₂/ Al ₂O ₃The mol ratio preferable range is 20～100 the crystal grain preferable range that contains the MCM-49 presoma amorphous substance in 10～400 nanometers, and the amount of seed preferable range is SiO ₂0.1～10% of weight.Control pH value preferable range is 8～14, and more preferably scope is 9～14.Used organic amine preferred version is to be selected from least a in hexamethylene imine, 4-propyl bromide, TPAOH, tetraethylammonium bromide, tetraethyl ammonium hydroxide, Tetrabutyl amonium bromide, TBAH, triethylamine, n-Butyl Amine 99, quadrol or the ethamine; Inorganic ammonium preferred version is to be selected from least a in ammoniacal liquor, the ammonium salt; When selecting mixed templates for use, mol ratio is 1: 1 or 1: 1: 1 (selecting three kinds of template for use); The pH value is regulated with dilute acid soln, and used dilute acid soln preferred version is to be selected from least a in dilute hydrochloric acid, dilute sulphuric acid, rare nitric acid, dilute phosphoric acid, oxalic acid or the acetate.The crystallization temperature preferable range is 100～200 ℃, and the crystallization time preferable range is 10～60 hours.

The synthetic method concrete operations of three-phase intergrowth molecular sieve are, get the silicon source and the aluminium source of aequum by material proportion, make solution with dissolved in distilled water respectively, then two kinds of solution are mixed, the powerful stirring, the template M that adds aequum then stirs after 30 minutes and regulates the pH value in 8～14 scopes with dilute acid soln, supplies distilled water again.Colloidal sol is put into autoclave, control required temperature, crystallization was taken out 4 hours, 550 ℃ roastings of 2 times, 120 ℃ oven dry of washing 3 hours after 10～100 hours, can obtain described ZSM-5/ mordenite/MCM-49 three-phase intergrowth molecular sieve.

The present invention is because the template that has adopted suitable two or more things of while to grow mutually, regulate and be fit to the pH value scope that related thing is grown mutually, control is fit to the silica alumina ratio and the crystallization temperature of growth, under hydrothermal condition, can in mixed sols, induce the crystal seed of several thing phases simultaneously, in the environment that is fit to their growths, generated this three-phase intergrowth molecular sieve then, because the surface and the interface of three-phase intergrowth molecular sieve, acid have than big difference with the simple mutually mechanical blended of thing with specific surface, its acid amount is bigger, acidity is stronger, contain multistage pore canal, so catalytic performance is preferably arranged, can handle the different mixture material of molecular diameter, can be used in the naphtha catalytic pyrolysis preparing ethylene propylene reaction, the diene quality total recovery of ethene and propylene can reach more than 55%, has obtained better technical effect.

Description of drawings

Fig. 1 is the XRD diffracting spectrum of synthetic three-phase intergrowth molecular sieve.

The present invention is further elaborated below by embodiment.

Embodiment

[embodiment 1]

Getting 1137 gram Starsos is dissolved in the 1800 gram deionized waters.In addition 89 gram Tai-Ace S 150 are dissolved in the 350 gram deionized waters, add in the sodium silicate solution under stirring.The mixed evenly back of solution is stirred and is added 158 gram hexamethylene imines down, and it is 11 that the pH value is regulated with 30% sulphuric acid soln in the back that stirs, and continues then to be stirred to evenly, carries out conventional hydrothermal crystallizing 12 hours under 150 ℃.Product after washing 130 ℃ dry 4 hours down, 550 ℃ of following roastings 3 hours promptly get MCM-49 crystal seed required for the present invention, remember and make M1.

[embodiment 2]

Method and content according to embodiment 1 is provided change the Tai-Ace S 150 add-on into 133.4 grams, make MCM-49 crystal seed required for the present invention, are designated as M2.

[embodiment 3]

Get 284 gram Starsos, become solution A with 300 gram dissolved in distilled water, get 16.7 gram Tai-Ace S 150, make solution B with 100 gram distilled water, B solution is slowly poured in the A solution, the powerful stirring, add 29.4 gram tetraethyl ammonium hydroxides and 19.9 gram hexamethylene imines (mixed templates is designated as M) then, after stirring for some time, regulate the pH value 11 with dilute sulphuric acid, the mole proportioning of control colloidal sol is: Si: Al: M: H ₂O=1: 0.05: 0.4: 40, add 3.0 gram MCM-49 crystal seed M1, mixing solutions is put into autoclave, 160 ℃ of insulations 40 hours, take out 4 hours, 550 ℃ roastings of 2 times, 120 ℃ oven dry of washing 3 hours then, make ZSM-5/ mordenite/MCM-49 coexisting material, the XRD diffracting spectrum as shown in Figure 1,13.51,12.26,11.22,9.97,8.82,7.74,6.14,5.14,4.15,3.90,3.71,3.45,3.20 there is d-spacing maximum value at 3.08,2.98 dust places.With the XRD diffraction quantitatively as can be known in the coexisting material mordenite weight percentage be 36.7%, ZSM-5 content is 44.7%, MCM-49 content is 18.6%.

[embodiment 4～8]

According to the method for embodiment 3, raw materials used as shown in table 4, the pH difference of control solution synthesizes ZSM-5/ mordenite/MCM-49 coexisting material respectively, sees Table 1.The XRD diffracting spectrum is identical with embodiment 3, and the ratio of mordenite, ZSM-5 and MCM-49 sees Table 3 in the coexisting material.

Table 1

Embodiment	The pH value of solution value	Sample number into spectrum
			Embodiment 4	8	FH-4

Embodiment 5	10	FH-5
			Embodiment 6	11	FH-6
Embodiment 7	13	FH-7
			Embodiment 8	14	FH-8

[embodiment 9～19]

According to the method for embodiment 3, raw materials used as shown in table 4, the different mole proportionings of control solution, synthetic ZSM-5/ mordenite/MCM-49 coexisting material sees Table 2 respectively.The XRD diffracting spectrum is identical with embodiment 3, and the ratio of mordenite, ZSM-5 and MCM-49 sees Table 3 in the coexisting material.

Table 2

Embodiment	Solution mole proportioning	Sample number into spectrum
			Embodiment 9	Si∶Al∶M∶H ₂O∶OH ^-1＝1∶0.002∶0.4∶40∶5	FH-9
Embodiment 10	Si∶Al∶M∶H ₂O∶OH ^-1＝1∶0.01∶0.4∶40∶0.01	FH-10
			Embodiment 11	Si∶Al∶M∶H ₂O∶OH ^-1＝1∶0.1∶0.1∶50∶0.001	FH-11
Embodiment 12	Si∶Al∶M∶H ₂O∶OH ^-1＝1∶0.125∶0.2∶40∶0.5	FH-12
			Embodiment 13	Si∶Al∶M∶H ₂O∶OH ^-1＝1∶0.01∶0.1∶40∶1.2	FH-13
Embodiment 14	Si∶Al∶M∶H ₂O∶OH ^-1＝1∶0.05∶2∶30∶0.1	FH-14
			Embodiment 15	Si∶Al∶M∶H ₂O∶OH ^-1＝1∶0.05∶3∶20∶1.8	FH-15
Embodiment 16	Si∶Al∶M∶H ₂O∶OH ^-1＝1∶0.167∶0.05∶60∶2	FH-16
			Embodiment 17	Si∶Al∶M∶H ₂O∶OH ^-1＝1∶0.2∶0.01∶80∶4	FH-17
Embodiment 18	Si∶Al∶M∶H ₂O∶OH ^-1＝1∶0.05∶0.4∶100∶6	FH-18
			Embodiment 19	Si∶Al∶M∶H ₂O∶OH ^-1＝1∶0.04∶0.4∶300∶10	FH-19

[embodiment 20～23]

According to the method for embodiment 3, raw materials used as shown in table 4, the mole proportioning of control solution is identical, selects mixed templates M for use, and mol ratio is 1: 1 or 1: 1: 1 (selecting three kinds of template for use), uses n-Butyl Amine 99 and hexamethylene imine successively respectively; Ethamine, quadrol and hexamethylene imine; Tetrem brometo de amonio and hexamethylene imine; Tetraethyl ammonium hydroxide, n-Butyl Amine 99 and hexamethylene imine, synthetic ZSM-5/ mordenite/MCM-49 coexisting material is designated as FH-20, FH-21, FH-22, FH-23 respectively.The XRD diffracting spectrum is identical with embodiment 3, and the ratio of mordenite, ZSM-5 and MCM-49 sees Table 3 in the coexisting material.

[embodiment 24～28]

According to the method for embodiment 3, raw materials used as shown in table 4, the mole proportioning of control solution is identical, and crystallization temperature is set to 80 ℃ respectively; 100 ℃; 130 ℃; 180 ℃ and 220 ℃, synthesized ZSM-5/ mordenite/MCM-49 coexisting material respectively, be designated as FH-24, FH-25, FH-26, FH-27 and FH-28.The XRD diffracting spectrum is identical with embodiment 3, and the ratio of mordenite, ZSM-5 and MCM-49 sees Table 3 in the coexisting material.

[embodiment 29～33]

According to the method for embodiment 3, raw materials used as shown in table 4, the mole proportioning of control solution is identical, and crystallization time is controlled to be 10 hours respectively; 20 hours; 60 hours; 100 hours and 200 hours, synthesized ZSM-5/ mordenite/MCM-49 coexisting material respectively, be designated as FH-29, FH-30, FH-31, FH-32 and FH-33.The XRD diffracting spectrum is identical with embodiment 3, and the ratio of mordenite, ZSM-5 and MCM-49 sees Table 3 in the coexisting material.

[embodiment 34～38]

According to the method for embodiment 3, raw materials used as shown in table 4, the mole proportioning of control solution is identical, adds M1 crystal seed amount and is respectively SiO in the raw material ₂0.01% of weight; 0.1%; 1%; 10% and 20%, synthesized ZSM-5/ mordenite/MCM-49 coexisting material respectively, be designated as FH-34, FH-35, FH-36, FH-37 and FH-38, the XRD diffracting spectrum is identical with embodiment 3, and the ratio of mordenite, ZSM-5 and MCM-49 sees Table 3 in the coexisting material.

Table 3

Sample number into spectrum	Mordenite content (weight %)	ZSM-5 content (weight %)	MCM-49 content (weight %)
				FH-3	36.7	44.7	18.6
FH-4	38.2	36.4	25.4
				FH-5	34.5	43.2	22.3
FH-6	24.1	49.5	26.4
				FH-7	16.2	55.5	28.3
FH-8	30.4	36.2	33.4
				FH-9	36.0	56.4	7.6
FH-10	32.3	39.4	28.3
				FH-11	36.2	34.5	29.3
FH-12	30.2	38.6	31.2
				FH-13	32.4	46.1	21.5
FH-14	33.2	35.3	31.5

FH-15	30.7	47.7	21.6
				FH-16	6.2	85.7	8.1
FH-17	7.6	84.8	7.6
				FH-18	24.1	50.3	25.6
FH-19	33.7	43.1	23.2
				FH-20	8.5	58.2	33.3
FH-21	12.0	50.1	37.9
				FH-22	35.1	25.1	29.8
FH-23	37.7	30.2	32.1
				FH-24	16.3	62.5	21.2
FH-25	19.7	55.7	24.6
				FH-26	31.0	38.5	30.5
FH-27	38.6	21.6	39.8
				FH-28	19.1	65.3	15.6
FH-29	10.3	42.9	46.8
				FH-30	18.4	46.2	35.4
FH-31	26.3	34.9	38.8
				FH-32	22.7	44.6	32.7
FH-33	20.3	39.2	41.5
				FH-34	44.6	50.6	4.8
FH-35	39.5	52.4	8.1
				FH-36	31.2	54.6	14.2
FH-37	26.9	36.4	36.7

FH-38

22.3

33.2

44.5

Table 4

Sample number into spectrum	Raw materials used
						The silicon source	The aluminium source	Template	Alkali source	Acid
	FH-4	Starso	Tai-Ace S 150	Quadrol, tetraethylammonium bromide	Sodium hydroxide						Dilute sulphuric acid
FH-5						Silicon sol	Sodium metaaluminate	N-Butyl Amine 99	Sodium hydroxide	Dilute hydrochloric acid
	FH-6	Soft silica	Pseudo-boehmite	Tetraethylammonium bromide	Sodium hydroxide						Rare nitric acid
FH-7						Silica gel	Bauxite	N-Butyl Amine 99	Sodium hydroxide	Oxalic acid
	FH-8	Diatomite	Aluminum hydroxide sol	Quadrol	Sodium hydroxide						Acetate
FH-9						Water glass	Tai-Ace S 150	Hexamethylene imine	Sodium hydroxide	Dilute hydrochloric acid
	FH-10	Tetraethoxy	Tai-Ace S 150	Tetraethylammonium bromide	Sodium hydroxide						Dilute hydrochloric acid
FH-11						Silicon sol	Aluminum nitrate	Ethamine, tetraethylammonium bromide	Sodium hydroxide	Dilute hydrochloric acid
	FH-12	Silicon sol	Aluminum chloride	Ethamine	Sodium hydroxide						Dilute sulphuric acid
FH-13						Silicon sol	Sodium aluminate	Tetraethylammonium bromide	Sodium hydroxide	Dilute sulphuric acid
	FH-14	Silicon sol	Tai-Ace S 150	Ethamine	Sodium hydroxide						Dilute sulphuric acid
FH-15						Silicon sol	Tai-Ace S 150	Hexamethylene imine	Potassium hydroxide	Dilute sulphuric acid
	FH-16	Silicon sol	Sodium aluminate	TPAOH	Potassium hydroxide						Dilute hydrochloric acid
FH-17						Starso	Sodium aluminate	4-propyl bromide	Potassium hydroxide	Dilute hydrochloric acid
	FH-18	Starso	Sodium aluminate	Tetraethyl ammonium hydroxide	Potassium hydroxide						Dilute hydrochloric acid
FH-19						Starso	Sodium aluminate	Tetraethylammonium bromide	Potassium hydroxide	Dilute hydrochloric acid
	FH-20	Starso	Sodium aluminate	N-Butyl Amine 99 and hexamethylene imine	Potassium hydroxide						Dilute sulphuric acid
FH-21						Starso, silicon sol	Sodium metaaluminate	Ethamine, quadrol and hexamethylene imine	Potassium hydroxide	Rare nitric acid

FH-22	Tetraethoxy, silicon sol	Sodium metaaluminate	Ammoniacal liquor and hexamethylene imine	Potassium hydroxide, sodium hydroxide	Dilute sulphuric acid, dilute hydrochloric acid
						FH-23	Tetraethoxy	Sodium metaaluminate, Tai-Ace S 150	Tetraethyl ammonium hydroxide, n-Butyl Amine 99 and hexamethylene imine	Potassium hydroxide, sodium hydroxide	Dilute sulphuric acid, dilute hydrochloric acid
FH-24	Tetraethoxy	Sodium metaaluminate, Tai-Ace S 150	Tetraethyl ammonium hydroxide	Potassium hydroxide, sodium hydroxide	Dilute sulphuric acid, dilute hydrochloric acid
						FH-25	Tetraethoxy	Sodium metaaluminate	Triethylamine	Potassium hydroxide	Rare nitric acid
FH-26	Water glass	Tai-Ace S 150	Triethylamine, tetraethylammonium bromide	Sodium hydroxide	Rare nitric acid
						FH-27	Water glass	Tai-Ace S 150	Tetraethylammonium bromide	Sodium hydroxide	Rare nitric acid
FH-28	Water glass	Sodium aluminate	Triethylamine	Sodium hydroxide	Rare nitric acid
						FH-29	Silica gel	Sodium aluminate	N-Butyl Amine 99	Sodium hydroxide	Rare nitric acid
FH-30	Soft silica	Sodium aluminate	TBAH	Sodium hydroxide	Rare nitric acid
						FH-31	Silica gel	Sodium aluminate	Tetrabutyl amonium bromide	Sodium hydroxide	Rare nitric acid
FH-32	Silica gel	Sodium aluminate	Ammoniacal liquor	Sodium hydroxide	Dilute sulphuric acid
						FH-33	Silicon sol	Sodium aluminate	Hexamethylene imine	Sodium hydroxide	Dilute sulphuric acid
FH-34	Silicon sol	Sodium aluminate	Ammoniacal liquor	Sodium hydroxide	Dilute sulphuric acid
						FH-35	Water glass	Tai-Ace S 150	Hexamethylene imine	Sodium hydroxide	Dilute sulphuric acid
FH-36	Starso	Sodium aluminate	Tetraethyl ammonium hydroxide	Potassium hydroxide	Rare nitric acid
						FH-37	Silicon sol	Sodium aluminate	Hexamethylene imine	Potassium hydroxide	Rare nitric acid
FH-38	Starso	Sodium aluminate	N-Butyl Amine 99	Sodium hydroxide	Rare nitric acid

[embodiment 39]

Getting embodiment 3 synthetic coexisting molecular sieves, is that 5% ammonium nitrate solution carries out ammonium exchange 3 hours at 90 ℃ with weight percentage.Product after filtration, washing, 130 ℃ be down after dry 3 hours, repeat an ammonium exchange again, washing after filtration,, 130 ℃ of following dryings are after 3 hours, 550 ℃ of following roastings 3 hours, make Hydrogen ZSM-5/ mordenite/MCM-49 coexisting molecular sieve, then compressing tablet, break into pieces, sieve, it is standby to get 20～40 purpose particles.With C ₄～C ₁₀Petroleum naphtha be raw material (the raw material physical index sees Table 6), be 12 millimeters fixed-bed reactor with diameter, 650 ℃, weight space velocity 0.5 hour ^-1, water/weight of oil is to check and rate under the condition of 0.02MPa than 3: 1, pressure, the ethene mass yield reaches 26.8%, the propylene mass yield reaches 29.4%, ethene and propylene diene quality total recovery reach 56.2%.

[embodiment 40]

Get embodiment 3 synthetic coexisting molecular sieves, the method for pressing embodiment 39 makes Hydrogen ZSM-5/ mordenite/MCM-49 coexisting molecular sieve.With the desorption curve of temperature programmed desorption(TPD) device mensuration ammonia, represent strength of acid with desorption temperature strong, the weak acid position.The ammonia that desorption goes out absorbs with excessive dilution heat of sulfuric acid through after the chromatogram, carries out back titration with standard solution of sodium hydroxide then, calculates the acid amount of tested molecular sieve thus.Measurement result such as table 5.

[comparative example 1]

The silica alumina ratio of getting the production of Shanghai petrochemical industry research institute is 40 ZSM-5 molecular sieve, measures its acidity by the method for embodiment 40, and the result is as shown in table 5.

[comparative example 2]

The silica alumina ratio of getting the production of Shanghai petrochemical industry research institute is 40 mordenite, measures its acidity by the method for embodiment 40, and the result is as shown in table 5.

[comparative example 3]

The silica alumina ratio of getting the production of Shanghai petrochemical industry research institute is 40 MCM-49 molecular sieve, measures its acidity by the method for embodiment 40, and the result is as shown in table 5.

[comparative example 4]

The silica alumina ratio of getting the production of Shanghai petrochemical industry research institute is mordenite/ZSM-5 coexisting molecular sieve of 40, and wherein the mordenite weight percentage is 15%, and the ZSM-5 weight percentage is 85%.Measure its acidity by the method for embodiment 40, the result is as shown in table 5.

Table 5

Embodiment or comparative example	Molecular sieve type	Weak acid position desorption temperature (℃)	The strong acidic site desorption temperature (℃)	Acid amount (* 10 ^-4Moles per gram)
					Embodiment 39	ZSM-5/ mordenite/MCM-49	305	512	12.82
Comparative example 1	ZSM-5	251	420	5.53
					Comparative example 2	Mordenite	241	522	11.06
Comparative example 3	MCM-49	255	422	9.3
					Comparative example 4	Mordenite/ZSM-5	284	495	11.40

Table 6 feed naphtha index

Project	Data
		Density (20 ℃) kilogram/rice ³	704.6
Boiling range is boiling range ℃ just	40
		Whole boiling range ℃	160
Saturated vapor pressure (20 ℃) kPa	50.2
		Alkane % (weight %)	65.18
Normal paraffin % (weight %) in the alkane	＞32.5
		Naphthenic hydrocarbon % (weight %)	28.44
Alkene % (weight %)	0.17
		Aromatic hydrocarbons % (weight %)	6.21

Claims

1. ZSM-5/ mordenite/MCM-49 three-phase intergrowth molecular sieve, the composition with following molar relationship: nSiO ₂: Al ₂O ₃, n=10 in the formula～1000 is characterized in that described material contains mordenite, three kinds of Symbionts of ZSM-5 and MCM-49 molecular sieve mutually, its XRD diffracting spectrum is included in 13.51 ± 0.1, and 12.26 ± 0.2,11.22 ± 0.2,9.97 ± 0.1,8.82 ± 0.1,7.74 ± 0.1,6.14 ± 0.1,5.14 ± 0.1,4.15 ± 0.1,3.90 ± 0.05,3.71 ± 0.1,3.45 ± 0.05,3.20 there is d-spacing maximum value at ± 0.05,3.08 ± 0.04,2.98 ± 0.05 dust places.

2. ZSM-5/ mordenite according to claim 1/MCM-49 three-phase intergrowth molecular sieve is characterized in that n=20～400.