CN1781600A - Method for preparing composite material containing Y-type molecular sieve - Google Patents

Abstract

The process of preparing composite material containing type-Y molecular sieve includes the following steps: the first synthesis of NaY molecular sieve guiding agent; the subsequent preparing molecular sieve gel with water glass, guiding agent, acid aluminum salt and sodium meta-aluminate; adding material capable of being used as carrier into the gel and crystallizing; and final filtering, washing and drying. The process results in compact combination between type-Y molecular sieve and the carrier and raised molecular sieve stability, and the prepared composite material may be modified as common molecular sieve and has medium holes specific surface area greater than 60 sq m/g and medium holes volume greater than 0.15 ml/g.

Description

A kind of preparation method who contains the Y zeolite composite

Technical field

The invention relates to a kind of preparation method who contains the composite of Y zeolite, in other words conj.or perhaps about a kind of preparation method of Y zeolite of load.

Background technology

As the core technology of petroleum refining industry, catalytic cracking receives much attention.Since Exxon company developed the first cover fluid catalytic cracking technology nineteen forty-two, the catalytic cracking development was very rapid.To 2000, working ability reached 702.8Mt/a.In China, 70%～80% gasoline comes catalytic cracking, and its effect in whole petroleum refining industry is crucial more.Current crude oil is heaviness, poor qualityization day by day; The further lighting of market demand product, clean; It is pollution-free that production requirement reaches, and do not have the greenization of discharging, and these have all proposed very big challenge to catalytic cracking.In view of this, the exploitation of all kinds of raw catelysts of catalytic cracking, new technology is in the ascendant.

Along with the heaviness day by day of the catalytically cracked material in the petroleum refining industry, average-size constantly increases at the proportion of big molecule hydrocarbon in raw material more than the 2nm.As the Y zeolite of the main active component of catalytic cracking catalyst, its aperture has only 0.7nm, obviously has a large amount of raw molecules can not enter the duct reaction of Y zeolite.Diffusion effect has remarkable influence to catalytic cracking reaction.In order to optimize the pore structure of catalyst, improve the accessibility of catalyst active center, improve the heavy oil conversion performance of catalyst, U.S. Pat P 3,367, disclose a kind of in 886 the spray-dried microspheroidal of making of the pretreated kaolin of process, then this kaolin microsphere matrix that contains pore structure is put into the synthetic liquid of NaY molecular sieve, under the hydrothermal synthesizing condition of routine, make the Y zeolite in-situ crystallization on the hole wall of kaolin microsphere matrix, directly make the method for catalytic cracking catalyst NaY/ kaolin microsphere.

After this USP 3,391,994; USP 3,663, and 165; USP 3,932, and 268; USP4,493,902; USP 4,581, and 341; USP 4,608, and 357; USP 4,790, and 929; USP 5,395, and 809; USP 5,559, and 067; WO 02/24329; US2003/0136707 then discloses a series of improvement projects to above-mentioned technology.Domestic also have some relevant these Study on Technology to report, comprising: CN 1057556C; CN 1064072C; CN 1067916C; CN 1179734A; CN 1195014A; CN 1232803A; CN 1334142A; CN 1334318A; CN 1393399A; CN 1429882A; CN 1429883A; Journal of Molecular Catalysis, 1995,9 (6): 424; Petroleum journal (PETROLEUM PROCESSING), 1996,12 (4): 20; Petroleum refining and chemical industry, 1997,28 (5): 51; Nonmetallic ore, 2003,26 (3): 6; Nonmetallic ore, 2002,25 (2): 22; China's non-metallic mineral industry guide, 2003,2:26; Industrial Catalysis, 2003,11 (5): 49; Ion-exchange and absorption, 1994,10 (3): 238; Liaoning chemical industry, 2000,29 (4): 199.Though they have all had certain improvement to this technology, be still USP 3,367 basically, disclosed flow process in 886.

In american petroleum NPRA (NPRA) in 2003 annual meeting, the advantage of this NaY/ kaolin microsphere composite catalyst in FCC processing of heavy oil process reduced: the pore structure that matrix had has been improved macromolecular diffusion of heavy oil and cracking performance; Because matrix duct surface is covered for the Y zeolite of in-situ crystallization, cracking is at outer surface of zeolite but not carry out the selectivity raising of cracking reaction on the amorphous ground substance in advance; The combination technique of this zeolite/matrix improves the conversion ratio of residual oil cracking reaction, and coke selectivity reduces.

Because preparation technology's limitation, this technology all exists tangible deficiency from preparation technology to the material property.Low and the modulation flexibly of this catalyst molecule sieve content at first, its molecular sieve content generally is controlled at 20-30%, and molecular sieve content is too high to make catalyst strength decline; Secondly, kaolin microsphere matrix is made up of the kaolin of different temperatures roasting, for taking into account molecular sieve content and catalyst strength, the content of the metakaolin of used low-temperature bake and high-temperature roasting soil must satisfy certain ratio, the result causes the framework silicon-aluminum of Y molecular sieve lower, generally has only about 4.6; In addition, from its preparation process as can be seen, this composite material preparation process complexity, production cost is higher.

In addition, CN1310039A discloses a kind of on porous tubing, the method for growth X type molecular screen membrane.Method with the precoating crystal seed also can be synthesized y-type zeolite membrane (chemical equipment technology, 2003,24 (4): 14-16 on porous ceramics; Ind.Eng.Chem.Res.1997,36:649-655; Separation and Purification Technology 2001,25:261-268).These all require molecular sieve to be grown on the inert carrier, form fine and close film, are used for gas, and liquid mixture adsorption is separated.

Summary of the invention

Purpose of the present invention is exactly to provide a kind of new preparation to contain the method for the composite of Y zeolite on the basis of existing technology, and a kind of method of Y zeolite of new preparation load is provided in other words conj.or perhaps.

Method provided by the invention comprises the steps:

(1) synthetic directed agents: according to the method for synthetic NaY molecular sieve guiding agent in the prior art, with sodium metasilicate, sodium metaaluminate, alkali lye and deionized water, according to (11～18) Na ₂O: Al ₂O ₃: (10～17) SiO ₂: (200～380) H ₂The mixed in molar ratio of O, after stirring, ℃ down aging a 0.5～48h makes crystallization director in room temperature to 70.

(2) system Y zeolite gel: according to (1.0～6.0) Na ₂O: Al ₂O ₃: (5.5～16) SiO ₂: (100～240) H ₂O, preferred (1.4～3.6) Na ₂O: Al ₂O ₃: (6～10) SiO ₂: (150～220) H ₂Total molar ratio of O adds directed agents, acid aluminium salt and the sodium metaaluminate that step (1) makes successively and stirs in waterglass; The Al in the directed agents wherein ₂O ₃Account for always feed intake in total Al ₂O ₃0.1～20wt% of amount, preferred 5～15wt%.

(3) molecular sieve and loaded article is compound: add the material that can be used as catalyst carrier in the gel that step (2) makes, total Al during wherein the addition of carrier should make the carrier amount and feed intake ₂O ₃The mol ratio of amount is 0.1～1000, and is preferred 5～200, is warming up to 90～120 ℃ after stirring, preferred 95～110 ℃ of crystallization, then after filtration, washing, drying obtain containing the composite of Y zeolite.

Directed agents in the inventive method can prepare by the whole bag of tricks of preparation faujasite directed agents in the prior art, but preferably prepares according to the at present industrial generally conventional preparation method of the NaY directed agents of employing.For example according to US3, the preparation method who is proposed in 639,099, US3,671,191 and US4,166,099 prepares, and guaranteeing constant product quality, and can keep technology and equipment not to do bigger change.

Said acid aluminium salt is selected from one of aluminum sulfate, aluminium chloride and aluminum nitrate in the inventive method, is preferably aluminum sulfate.Aluminium in sodium metaaluminate and acid aluminium salt and the directed agents is jointly as the aluminium source of NaY molecular sieve compositions material.Silicon in waterglass and the directed agents is jointly as the silicon source of NaY molecular sieve compositions material.The basicity that the sodium metaaluminate of acid aluminium salt and alkalescence can be used to regulate total material, the two ratio requires to decide according to the basicity of total material, should make the mixture that always feeds intake meet (1.0～6.0) Na ₂O: Al ₂O ₃: (5.5～16) SiO ₂: (100～240) H ₂O, preferred (1.4～3.6) Na ₂O: Al ₂O ₃: (6～10) SiO2: (150～220) H ₂Total molar ratio of O.Na in the above-mentioned formula ₂O represents the basicity of mixture, and it does not comprise the part that is neutralized by acid.In addition, also can be by adding acid or alkali is regulated basicity, but preferably adjust basicity according to the two ratio of the sodium metaaluminate of acid aluminium salt and alkalescence.

The said material that can be used as catalyst carrier can be selected from unformed SiO in the inventive method ₂Or Alusil, various Al ₂O ₃Or its presoma, various high-temperature inorganic oxide and clay.Wherein said Al ₂O ₃Be selected from α-Al ₂O ₃, γ-Al ₂O ₃, θ-Al ₂O ₃, η-Al ₂O ₃Wherein said Al ₂O ₃Presoma be selected from boehmite, boehmite, α-gibbsite, β-gibbsite; Wherein said high-temperature inorganic oxide is selected from ZrO ₂, AlPO ₄, TiO ₂Wherein said clay is selected from kaolin, imvite, hydrotalcite, spinelle, attapulgite.

As everyone knows, after molecular sieve and carrier were mixed and made into catalyst, its stability obviously was better than independent molecular sieve.This is owing in ageing process, between molecular sieve and the carrier mass exchange takes place, and has reduced high temperature and the steam destruction to molecular sieve structure.Here it is usually said carrier is to the protective effect of molecular sieve.Method provided by the invention grows into Y zeolite on the carrier in building-up process, and molecular sieve combines tightr with carrier, is expected to further strengthen the interaction between carrier and the molecular sieve, improves the stability of molecular sieve.

Y zeolite is grown in the surface of carrier in the composite that contains Y zeolite that method provided by the invention is synthesized, and therefore, the mesoporous surface of carrier is covered by molecular sieve.As previously mentioned, the mesoporous surface of catalyst is covered by Y zeolite, and the big pre-cracking of molecule is at outer surface of zeolite but not when carrying out on the amorphous ground substance, the selectivity of cracking reaction improves, and heavy oil conversion performance is strong, and coke selectivity reduces.Method provided by the invention is to synthesize to contain mesoporous Y zeolite composite, and it can carry out various modifications as common molecular sieve, and the consumption in catalyst can be adjusted arbitrarily, can be compound with multiple catalyst carrier, have modulation flexibly.

The composite that contains Y zeolite that the inventive method synthesizes, its total specific area is greater than 400m ²/ g is usually greater than 600m ²/ g; Its aperture is that the middle pore specific surface area of 10～100nm is greater than 20m ²/ g is usually greater than 60m ²/ g; Mesopore volume is greater than 0.1ml/g, usually greater than 0.15ml/g.

Description of drawings

Fig. 1 is catalytic cracking catalyst NaY/ kaolin microsphere preparation method's a simplified flow chart.

In the accompanying drawing, kaolin through mixing making beating 2, through pipeline 3 process spray-dryings 4, is made kaolin microsphere through pipeline 1 again.Kaolin microsphere reacts in reactor 7 through piping 5 and through the synthetic liquid of the NaY of pipeline 6 molecular sieve, flows out through pipeline 8, obtains the NaY/ kaolin microsphere.

The specific embodiment

The following examples will the present invention is further illustrated, but not thereby limiting the invention.

Comparative Examples 1

The explanation of this Comparative Examples prepares Y zeolite according to conventional method.

Get 100ml waterglass (Chang Ling oil-refining chemical factory catalyst plant product, proportion 1.26, SiO ₂Content 255.8g/L, modulus 3.24) put into beaker, add the high sodium aluminate solution of 70.7g (Chang Ling oil-refining chemical factory catalyst plant product, proportion 1.33, Al ₂O ₃Content 41g/L, Na ₂O content 280g/L), after mixing, in aged at room temperature 24h, promptly get required directed agents, its mole proportioning is 16Na ₂O: Al ₂O ₃15SiO ₂: 320H ₂O.

The NaY molecular sieve is according to 2.76Na ₂O: Al ₂O ₃: 8.4SiO ₂: 209H ₂The proportioning of O is synthetic.Stir down, successively with 370ml deionized water, 165g directed agents, 247ml aluminum sulfate solution (Chang Ling oil-refining chemical factory catalyst plant product, proportion 1.28, Al ₂O ₃Content 88.2g/L) and 200ml low sodium aluminate solution (Chang Ling oil-refining chemical factory catalyst plant product, proportion 1.23, Al ₂O ₃Content 102g/L, Na ₂O content 151.9g/L) be added in the 780ml waterglass (specification is the same), add the back and continue strong agitation 30min, behind 100 ℃ of static crystallization 33h, stop crystallization, product after filtration, washing, oven dry promptly get Y zeolite.

Record the SiO of this Y zeolite product with x-ray diffraction method ₂/ Al ₂O ₃Be 5.21, and the degree of crystallinity that records is decided to be 100%.It is 728m that the BET method records total specific area ²/ g, wherein middle pore specific surface area is 6m ²/ g, mesopore volume is 0.05mL/g.

Embodiment 1

The present embodiment explanation is the composite that carrier material contains Y zeolite according to method preparation provided by the invention with the boehmite.

Get 100ml waterglass (Chang Ling oil-refining chemical factory catalyst plant product, proportion 1.26, SiO ₂Content 255.8g/L, modulus 3.24) put into beaker, add the high sodium aluminate solution of 70.7g (Chang Ling oil-refining chemical factory catalyst plant product, proportion 1.33, Al ₂O ₃Content 41g/L, Na ₂O content 280g/L), after mixing, in aged at room temperature 24h, promptly get required directed agents, its mole proportioning is 16Na ₂O: Al ₂O ₃: 15SiO ₂: 320H ₂O.

The NaY molecular sieve is according to 2.76Na ₂O: Al ₂O ₃: 8.4SiO ₂: 209H ₂The proportioning of O is synthetic.Stir down, successively with 370ml deionized water, 165g directed agents, 247ml aluminum sulfate solution (Chang Ling oil-refining chemical factory catalyst plant product, proportion 1.28, Al ₂O ₃Content 88.2g/L) and 200ml low sodium aluminate solution (Chang Ling oil-refining chemical factory catalyst plant product, proportion 1.23, Al ₂O ₃Content 102g/L, Na ₂O content 151.9g/L) is added in the 780ml waterglass (specification is the same), adds the back and continue strong agitation 30min.

With 400g boehmite (Chalco Shandong branch company product, trade names are HF-159) add in the above-mentioned gel, continue strong agitation 3h, again in 100 ℃ of static crystallization 33h, stop crystallization, product after filtration, washing, oven dry promptly get the composite that contains Y zeolite.

It is 96% (degree of crystallinity with Comparative Examples 1 sample is standard meter, down together) that this composite sample records its relative crystallinity with x-ray diffraction method, SiO ₂/ Al ₂O ₃Be 5.18, it is 712m that the BET method records total specific area ²/ g, wherein middle pore specific surface area is 83m ²/ g, mesopore volume is 0.135mL/g.

Embodiment 2

The present embodiment explanation is the composite that carrier material contains Y zeolite according to method preparation provided by the invention with diatomite.

In pressing the NaY molecular sieve synthesized gel rubber of embodiment 1 preparation, 2000g adds 600g diatomite (Qingdao Samsung diatomite Co., Ltd product, trade names are AG-JXA), after stirring, behind 100 ℃ of static crystallization 32h, stop crystallization, product after filtration, washing, oven dry promptly get the composite that contains Y zeolite.

It is 89% that this composite sample records its relative crystallinity with x-ray diffraction method, SiO ₂/ Al ₂O ₃Be 5.12.It is 684m that the BET method records total specific area ²/ g, wherein middle pore specific surface area is 112m ²/ g, mesopore volume is 0.168mL/g.

Embodiment 3

The present embodiment explanation is the composite that carrier material contains Y zeolite according to method preparation provided by the invention with α-gibbsite.

In pressing the NaY molecular sieve synthesized gel rubber of embodiment 1 preparation, 2000g adds 1000g α-gibbsite (Chalco Shandong branch company product, trade names are AH-1), stir the back in 40 ℃ of aging 15h, again behind 100 ℃ of static crystallization 28h, stop crystallization, product after filtration, washing, oven dry promptly get the composite that contains Y zeolite.

It is 86% that this composite sample records its relative crystallinity with x-ray diffraction method, SiO ₂/ Al ₂O ₃Be 5.03.It is 595m that the BET method records total specific area ²/ g, wherein middle pore specific surface area is 94m ²/ g, mesopore volume is 0.144mL/g.

Embodiment 4

The present embodiment explanation prepares with γ-Al according to method provided by the invention ₂O ₃The composite that contains Y zeolite for carrier material.

In pressing the NaY molecular sieve synthesized gel rubber of embodiment 1 preparation, 2000g adds 100g γ-Al ₂O ₃(getting through 550 ℃ of roastings) by embodiment 1 used boehmite, the back that stirs behind 100 ℃ of static crystallization 35h, stops crystallization again in 80 ℃ of aging 2h, and product is after filtration, washing, oven dry promptly get the composite that contains Y zeolite.

It is 101% that this composite sample records its relative crystallinity with x-ray diffraction method, SiO ₂/ Al ₂O ₃Be 5.15.It is 731m that the BET method records total specific area ²/ g, wherein middle pore specific surface area is 52m ²/ g, mesopore volume is 0.112mL/g.

Embodiment 5

The present embodiment explanation is the composite that carrier material contains Y zeolite according to method preparation provided by the invention with kaolin.

In pressing the NaY molecular sieve synthesized gel rubber of embodiment 1 preparation, 2000g adds 300g kaolin (China Kaolin Co., Ltd's product, trade names are S-1), after stirring, behind 100 ℃ of static crystallization 35h, stop crystallization, product after filtration, washing, oven dry promptly get the composite that contains Y zeolite.

It is 97% that this composite sample records its relative crystallinity with x-ray diffraction method, SiO ₂/ Al ₂O ₃Be 5.25.It is 708m that the BET method records total specific area ²/ g, wherein middle pore specific surface area is 28m ²/ g, mesopore volume is 0.105mL/g.

Claims (10)

1, a kind of preparation method who contains the Y zeolite composite comprises the steps:

(1) synthetic directed agents: according to the method for synthetic NaY molecular sieve guiding agent in the prior art, with sodium metasilicate, sodium metaaluminate, alkali lye and deionized water, according to (11～18) Na ₂O: Al ₂O ₃: (10～17) SiO ₂: (200～380) H ₂The mixed in molar ratio of O, after stirring, ℃ down aging a 0.5～48h makes crystallization director in room temperature to 70;

(2) system Y zeolite gel: according to (1.0～6.0) Na ₂O: Al ₂O ₃: (5.5～16) SiO ₂: (100～240) H ₂Total molar ratio of O adds directed agents, acid aluminium salt and the sodium metaaluminate that step (1) makes successively and stirs in waterglass; The Al in the directed agents wherein ₂O ₃Account for always feed intake in total Al ₂O ₃0.1～20wt% of amount;

(3) molecular sieve and loaded article is compound: add the material that can be used as catalyst carrier in the gel that step (2) makes, total Al during wherein the addition of carrier should make the carrier amount and feed intake ₂O ₃The mol ratio of amount is 0.1～1000, is warming up to 90～120 after stirring.℃ crystallization, then after filtration, washing, drying.

2,, be in the wherein said step (2) according to (1.4～3.6) Na according to the preparation method of claim 1 ₂O: Al ₂O ₃: (6～10) SiO ₂: (150～220) H ₂Total molar ratio system Y zeolite gel of O, the Al in the directed agents wherein ₂O ₃Account for always feed intake in total Al ₂O ₃5～15wt% of amount.

3, according to the preparation method of claim 1, total Al during the addition that wherein said step (3) can be used as catalyst carrier material should make the carrier amount and feed intake ₂O ₃The mol ratio of amount is 5～200, is warming up to 95～110 ℃ of crystallization after stirring.

4, according to the preparation method of claim 1, wherein said acid aluminium salt is selected from one of aluminum sulfate, aluminium chloride and aluminum nitrate.

5, according to the preparation method of claim 4, wherein said acid aluminium salt is selected from aluminum sulfate.

6, according to the preparation method of claim 1, the wherein said material that can be used as catalyst carrier is selected from unformed SiO ₂Or Alusil.

7, according to the preparation method of claim 1, the wherein said material that can be used as catalyst carrier is selected from α-Al ₂O ₃, γ-Al ₂O ₃, θ-Al ₂O ₃And η-Al ₂O ₃One of Al ₂O ₃

8, according to the preparation method of claim 1, the wherein said material that can be used as catalyst carrier is selected from the Al of one of boehmite, boehmite, α-gibbsite and β-gibbsite ₂O ₃Presoma.

9, according to the preparation method of claim 1, the wherein said material that can be used as catalyst carrier is selected from ZrO ₂, AlPO ₄And TiO ₂One of high-temperature inorganic oxide.

10, according to the preparation method of claim 1, the wherein said material that can be used as catalyst carrier is selected from the clay of one of kaolin, imvite, hydrotalcite, spinelle and attapulgite.