CN100358807C

CN100358807C - Selective preparation method for zeolite

Info

Publication number: CN100358807C
Application number: CNB2004100527228A
Authority: CN
Inventors: 王德举; 唐颐; 刘仲能; 谢在库; 夏建超
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: 2004-07-12
Filing date: 2004-07-12
Publication date: 2008-01-02
Anticipated expiration: 2024-07-12
Also published as: CN1721326A

Abstract

The present invention relates to a method for selectively preparing NaX zeolite, which mainly solves the problem of selectively preparing NaX zeolite by utilizing minerals or waste slags containing Si and Al components. The method solves the problem in a better way by adopting the technical scheme that waste slags containing Si and Al components are used as Si and Al raw materials; a crystallization system is formed by the Si and Al raw materials and an alkali solution; amorphous Si and Al mixed gel is added into the crystallization system to be used as a guiding agent; the molar proportion of the guiding agent comprises aNa2O, Al2O3, bSiO2 and dH2O, wherein a is from 9 to 12, b is from 8 to 15, and d is from 150 to 300; NaX zeolite is obtained under the conditions of crystallization temperature of 60 to 120 DEG C and crystallization time of 6 to 72 hours. The method can be used in the industrial preparation of NaX zeolite.

Description

Selectivity prepares the method for zeolite

Technical field

The present invention relates to the method that a kind of selectivity prepares the NaX zeolite, particularly prepare the method for NaX zeolite about the residue waste residue selectivity of utilizing kaolin, coal gangue, bauxite to produce polymerize aluminum chloride.

Background technology

Zeolite is a kind of crystalline silico-aluminate, has that specific surface area is big, hydrothermal stability is high, micropore enriches equal first-class performance, is widely used as catalyzer, sorbent material, ion-exchanger and new function material.The NaX zeolite has bigger loading capacity and ion-exchange capacity, gas adsorption with the field such as separate and seem very important.How the X type molecular sieve of industrial application is with highly active industrial chemicals hydro-thermal synthetic.If with the natural aluminosilicate mineral is raw material, can reduce production costs greatly.

Kaolin, coal gangue, bauxite etc. are rich in the mineral of aluminium silicon components, and main component is the oxide compound of silicon, aluminium etc., and these mineral often are used to extract metallic aluminium, aluminum oxide and other aluminium salt, also are to produce water purification agent polymerize aluminum chloride good raw material.It is soft silica and a spot of quartz and kaolin composition that these mineral are produced polymerize aluminum chloride institute waste discharge slag main component, and the aluminum oxide that is not leached and a spot of material that can not transform, and the resource that can be used as synthetic zeolite is used.But a lot of producers do not handle, and just simple the stacking caused the environmental pollution and the wasting of resources.Directly utilize these mineral the zeolite of extensive use to be arranged, have important social benefit and economic benefit as feedstock production.Can prepare NaA zeolite [Lin Xianzhang, synthetic 4A zeolite of kaolin and preparation method thereof, Chinese patent, CN1124716] from these mineral through simple processing.Ni Zheng etc. have then prepared NaX zeolite [Ni Zheng by the method for alkali fusion processing coal gangue, Tang's chin or cheek, Hua Weiming, produce NaX type zeolite [J] by coal gangue. petrochemical complex, 2000,29 (5), 336-340] though this method can obtain purified NaX zeolite, but the condition harshness of alkali fusion, the energy consumption height also has certain distance from practical application.

Summary of the invention

Technical problem to be solved by this invention is not relate to the problem that the waste residue that utilizes the silicon-aluminum containing composition prepares the NaX zeolite in the conventional art, provides a kind of new selectivity to prepare the method for NaX zeolite.This method has can make full use of silicon-aluminum containing composition waste residue, the synthetic low advantage of NaX zeolite cost.

For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of selectivity prepares the method for NaX zeolite, waste residue with the silicon-aluminum containing composition is the sial raw material, sial raw material and concentration are that the alkaline solution of 1～4 mol is formed the crystallization system, the non-crystalline state sial mixed gel directed agents that in the crystallization system, adds system gross weight 2～10%, at crystallization temperature is that crystallization obtained the NaX zeolite in 6～72 hours under 60～120 ℃ of conditions, and wherein directed agents mole proportioning is: aNa ₂O: Al ₂O ₃: bSiO ₂: dH ₂O, the span of a is 9～12, and the span of b is 8～15, and the span of d is 150～300, and the waste residue of described silicon-aluminum containing composition is selected from the residue waste residue after kaolin, coal gangue or bauxite are produced polymerize aluminum chloride.

In the technique scheme, the value preferable range of a is 10.5～11.5, and the value preferable range of b is 9～11, and the value preferable range of d is 160～200.The consumption preferable range of adding directed agents in the crystallization system is 3～7% of a system gross weight, the crystallization temperature preferable range is 70～110 ℃, the crystallization time preferable range is 12～48 hours, and the concentration preferable range of alkaline solution is 1～3 mol, and the preferred version of alkali is selected from NaOH.

Here be example explanation the inventive method with following siulica-alumina mineral: kaolin is provided by molecular sieve factory in the brocade of Shanghai, has 2SiO ₂Al ₂O ₃2H ₂The mole of O is formed; Coal gangue is taken from Shanxi ternary coal industry company limited, and predominant quantity percentage ratio is Al ₂O ₃13.1%, SiO ₂25.8%, C 49.38%, and H 3.10%, and N 0.98%, Fe ₂O ₃0.43%; Be that waste residue behind the poly-and aluminum chloride of raw material production is taken from east wind chemical plant, the Huaibei, Anhui with bauxite.Actual conditions is as follows:

1, the preparation of directed agents: with NaOH, NaAlO ₂Be mixed in proportion dissolving with distilled water, add the silicon sol of aequum then, at room temperature stirred aging 1 day, the preparation directed agents, the directed agents mole consists of: 10.67Na ₂O: Al ₂O ₃: 10SiO ₂: 180H ₂O.

2, kaolin is in 600 ℃ of following roastings 2 hours activation, with the mixed in hydrochloric acid of an amount of 20% weight 90 ℃ of airtight heating 4 hours, filter then, washing is dry; Coal gangue is in 900 ℃ of following roastings activation in 4 hours; Bauxite production waste residue poly-and aluminum chloride activated 600 ℃ of following roastings in 2 hours.

3, hydrothermal crystallizing: take by weighing above-mentioned 1 gram solid matter respectively and mix with the NaOH solution of 8 milliliters 2 mol and stir agingly, add the directed agents of 5% weight, transfer to then in the reactor 100 ℃ of following crystallization 12～48 hours.

4, product washing and dry: wash zeolite product with water near neutral, be drying to obtain powdery product at a certain temperature.

Among the present invention, because the waste residue with the silicon-aluminum containing composition is the sial raw material, more specifically saying so with the residue waste residue that is selected from kaolin, coal gangue or bauxite production polymerize aluminum chloride is the synthetic NaX zeolite of sial raw material, therefore preparation cost is low on the one hand, raw material resources have been made full use of on the other hand, reduced the influence of waste residue, obtained better technical effect environment.

Description of drawings

Fig. 1 is the XRD figure spectrum of embodiment 1～4 product.

Fig. 2 is the SEM figure of embodiment 3 products.

Fig. 3 is the XRD figure spectrum of embodiment 5～8 products.

Fig. 4 is the XRD figure spectrum of embodiment 9～12 products.

Fig. 5 is the XRD figure spectrum of embodiment 17～19 products.

Namely to leach the later kaolin of al composition as raw material, the hydrothermal treatment consists different time is prepared after the interpolation directed agents for Fig. 1 The XRD collection of illustrative plates of zeolite. After through 12 hours hydrothermal treatment consists, without any the crystalline phase peak appearance (Figure 1A) of zeolite, The crystalline phase peak of FAU zeolite clearly occurs after 24 hours, and does not have other zeolite stray crystal (Figure 1B), 32 After hour hydrothermal treatment consists, the degree of crystallinity of FAU zeolite reaches maximum (Fig. 1 C), continues to prolong crystallization time again, and FAU boils The degree of crystallinity of stone no longer increases, and (Fig. 1 D) on the contrary to some extent descends.

Can find out by the SEM photo among Fig. 2 that after 32 hours hydrothermal treatment consists, raw material basically all has been converted into and has boiled Stone, the FAU zeolite crystal of generation is octahedral structure, grain size is at 2～10 microns.

Gangue, with identical crystallization condition, adds directed agents and carries out the hydro-thermal place after 4 hours 900 ℃ of roastings among Fig. 3 Reason, after through 12 hours hydrothermal treatment consists, clearly the appearance of the crystalline phase peak of FAU zeolite, and do not have it Its zeolite stray crystal (Fig. 3 A). Prolong crystallization time, the degree of crystallinity of FAU zeolite continued to increase (Fig. 3 B), 20 hours hydro-thermals After the processing, the degree of crystallinity maximum of FAU zeolite also be can't see unformed diffuse peaks (Fig. 3 C), again from the XRD collection of illustrative plates Continue to prolong crystallization time, the degree of crystallinity of FAU zeolite no longer increases (Fig. 3 D).

Through after 12 hours the hydrothermal treatment consists, the crystalline phase peak of FAU zeolite significantly occurs among Fig. 4, and has few Amount stray crystal (Fig. 9 A). Prolong crystallization time, the degree of crystallinity of FAU zeolite continues to increase, after 24 hours hydrothermal treatment consists, The degree of crystallinity maximum of FAU zeolite, but (Fig. 9 B) also appears in another kind of crystalline phase P zeolite. Continue again to prolong crystallization time, The degree of crystallinity of FAU zeolite no longer increases, and descends to some extent on the contrary, and the P zeolite crystallinity then continues to increase (Fig. 9 C, 9D), The FAU zeolite changes to the P zeolite gradually.

The result shows the later kaolin of acidleach in the situation that does not have directed agents to add among Fig. 5, and hydrothermal treatment consists is after 32 hours There is not zeolite to generate (Fig. 5 A). Not adding directed agents without the kaolin of acidleach after the roasting directly carries out hydrothermal treatment consists and produces later on Thing is the NaA zeolite (Fig. 5 B) of high-crystallinity. Hydrothermal Method from Kaolin without acidleach after the roasting was processed 32 hours, even have Product remains NaA zeolite (Fig. 5 C) in the situation that directed agents adds. Show that directed agents only closes at the reaction system silica alumina ratio Just can play guide effect in the time of suitable. Behind part al composition in the acidleach removal kaolin, the reaction system silica alumina ratio raises, Under the effect of directed agents, can generate target FAU zeolite. On the contrary, the kaolin that acidleach is later is not led if do not add To agent, even other condition is all identical, there is not the generation of target NaX zeolite yet.

Table 1 is the ion-exchange degree of several preparation zeolite products.

The ion-exchange degree of table 1 preparation zeolite product

Sample number into spectrum	A	B	C	D	E
Sample number into spectrum	A	B	C	D	E	CEC (mM/100 grams)	154	57	86	101	303

ABCD prepares the sample crystalline substance for adding directed agents: the Hydrothermal Method from Kaolin of leaching al composition is processed 32 hours (A), roasting gangue hydro-thermal Process 24 hours (B) roasting waste residue water heat treatment 24 hours (C) and 48 hours (D).

Utilize kaolin, coal gangue, bauxite to produce polymerize aluminum chloride residue waste residue below by embodiment to the present invention, add the directed agents selectivity through pre-treatment and prepare the further instruction that the method for NaX zeolite is done.

Embodiment

[embodiment 1～4]

It is aging with the NaOH solution mixing stirring of 8 milliliters 2 mol to take by weighing the pretreated solid matter of above-mentioned 1 gram kaolin respectively, adds the directed agents of 5% weight, and the directed agents mole consists of 10.67Na ₂O: Al ₂O ₃: 10SiO ₂: 180H ₂O transfers in the reactor then 100 ℃ of crystallization 12 hours respectively down, 24 hours, 36 hours, 48 hours, filters then, washs, drying obtains product.The product characterization result is seen Fig. 1, Fig. 2.

[embodiment 5～8]

It is aging with the NaOH solution mixing stirring of 8 milliliters 2 mol to take by weighing the pretreated solid matter of above-mentioned 1 gram coal gangue respectively, adds the directed agents of 5% weight, and the directed agents mole consists of 11Na ₂O: Al ₂O ₃: 10.5SiO ₂: 190H ₂O transfers in the reactor then 100 ℃ of crystallization 12 hours respectively down, 16 hours, 20 hours, 24 hours, filters then, washs, drying obtains the NaX zeolite product.The product characterization result is seen Fig. 3.

[embodiment 9～12]

The pretreated solid matter of waste residue that takes by weighing the poly-and aluminum chloride of above-mentioned 1 gram bauxite production respectively mixes with the NaOH solution of 8 milliliters 2 mol and stirs agingly, adds the directed agents of 5% weight, and the directed agents mole consists of 11.3Na ₂O: Al ₂O ₃: 9.5SiO ₂: 170H ₂O transfers in the reactor then 100 ℃ of crystallization 12 hours respectively down, 24 hours, 36 hours, 48 hours, filters then, washs, drying obtains zeolite product.Product XRD figure spectrum is seen Fig. 4.

[embodiment 13～16]

By example 1～4 described method the pretreated solid matter of kaolin is transformed, the hydrothermal crystallizing temperature is respectively 70 ℃, 80 ℃, 90 ℃, 110 ℃, and crystallization time is 36 hours, and other conditions are constant, and products obtained therefrom is the NaX zeolite.

[embodiment 17～19]

For investigating directed agents and acidleach influence, respectively roasting kaolin is not added directed agents, roasting kaolin later in acidleach and do not add directed agents and roasting kaolin without acidleach yet and add directed agents without acidleach and carried out hydrothermal treatment consists 32 hours zeolite product.All can not obtain NaX zeolite (see figure 5) under three kinds of situations as a result.

[embodiment 20]

Take by weighing above-mentioned 1 gram coal gangue pretreated solid matter and mix with the NaOH solution of 8 milliliters 2 mol and stir agingly, do not add directed agents, 100 ℃ of following crystallization 20 hours, the product that obtains was the mixture of NaA and NaX zeolite in reactor.

Claims

1, a kind of selectivity prepares the method for NaX zeolite, waste residue with the silicon-aluminum containing composition is the sial raw material, sial raw material and concentration are that the alkaline solution of 1～4 mol is formed the crystallization system, the non-crystalline state sial mixed gel directed agents that in the crystallization system, adds system gross weight 2～10%, at crystallization temperature is that crystallization obtained the NaX zeolite in 6～72 hours under 60～120 ℃ of conditions, and wherein directed agents mole proportioning is: aNa ₂O: Al ₂O ₃: bSiO ₂: dH ₂O, the span of a is 9～12, and the span of b is 8～15, and the span of d is 150～300, and the waste residue of described silicon-aluminum containing composition is selected from the residue waste residue after kaolin, coal gangue or bauxite are produced polymerize aluminum chloride.

2, the method for preparing the NaX zeolite according to the described selectivity of claim 1, the span that it is characterized in that a is 10.5～11.5, and the span of b is 9～11, and the span of d is 160～200.

3, the method for preparing the NaX zeolite according to the described selectivity of claim 1 is characterized in that the consumption of interpolation directed agents in the crystallization system is 3～7% of a system gross weight.

4, the method for preparing the NaX zeolite according to the described selectivity of claim 1 is characterized in that crystallization temperature is 70～110 ℃, and crystallization time is 12～48 hours.

5, the method for preparing the NaX zeolite according to the described selectivity of claim 1 is characterized in that the concentration of alkaline solution is 1～3 mol, and alkali is selected from NaOH.