CN101817539A - Method for synthesizing A type molecular sieve by adopting attapulgite clay - Google Patents

Abstract

The invention relates to a method for synthesizing an A type molecular sieve by adopting attapulgite clay, comprising the following steps of: selecting the attapulgite clay containing iron less than 5 percent, and matching the attapulgite clay according to the mole ratio of Na2O:Al2O3:SiO2:H2O=3:1:2:185; adding to an NaOH solution of 4 mol/L; equally dividing the NaOH solution to two containers which are respectively marked as a No. 1 container and a No. 2 container; placing the attapulgite clay containing the iron less than 5 percent into the No. 1 container, and stirring at the temperature of 80-90 DEG C and constant speed for 1 hour; adding sodium aluminate to the No. 2 container to be dissolved till the solution is clear, then fast pouring into the No. 1 container, and stirring at the temperature of 30-40 DEG C for 30 minutes to form gel; placing into a baking oven for sealing, and then crystallizing for 3.5 hours at the temperature of 90-100 DEG C for 3.5 hours; carrying out solid-liquid separation on a crystalline solid product through filtering; washing the crystalline solid product till pH is less than 9 by using deionized water; and drying at the temperature of 80-110 DEG C for more than 12 hours to obtain the A type molecular sieve.

Description

Adopt the method for the synthetic A type molecular sieve of attapulgite clay

Technical field

The present invention relates to adopt attapulgite clay to prepare the method for A type molecular sieve.

Background technology

China be the main attapulgite clay in the world main contain state and producing country, its main component silico-aluminate.Molecular sieve is a kind of silico-aluminate of crystal form, and its spacial framework is by silicon-oxy tetrahedron unit [SiO ₄] and aluminum-oxygen tetrahedron [AlO ₄] unit is staggered and forms, its structure is very similar to NaCl, and its chemical group journey general formula is Na ₂O: Al ₂O ₃: 2SiO ₂: 5H ₂O belongs to isometric system.Because its uniform pore size and big area exist large quantity of moisture and positively charged ion in structure, this construction features make molecular sieve have absorption, catalysis and the ion-exchange three big characteristics of selection.Therefore be widely used in industries such as oil, chemistry, metallurgy.The method of producing at present 4A type molecular sieve has chemical feedstocks preparation method (being complete synthesizing process) and with clay preparation method (being semi-synthesis method).People such as Hewell at first utilize kaolin to synthesize the 4A molecular sieve, be the extensive attention that the method for the synthetic 4A molecular sieve of raw material has been subjected to Chinese scholars subsequently with the natural mineral, successively utilize crude substance such as diatomite, perlite, bauxite, wilkinite to successfully synthesize the 4A molecular sieve, but domestic do not see attapulgite clay mining in the study on the synthesis of 4A molecular sieve.

Summary of the invention

The purpose of this invention is to provide a kind of method that adopts the synthetic A type molecular sieve of attapulgite clay.

The present invention is the method that adopts the synthetic A type molecular sieve of attapulgite clay, the steps include:

(1) select for use or iron content at the attapulgite clay below 5%, silicone content is 40～70% in its attapulgite clay ore deposit, the content of aluminium is 6～18%; Selecting content for use is sodium aluminate more than 95%, and content is the sodium hydroxide more than 95%;

(2) Na in molar ratio ₂O: Al ₂O ₃: SiO ₂: H ₂O is 3: 1: 2: 185 apolegamys join above-mentioned attapulgite clay in the NaOH solution of 4mol/L with it, stir 10～20 minutes to all dissolving, and solution all is placed in two containers, are denoted as No. 1 container, No. 2 containers;

(3) with iron-holder in the attapulgite clay below 5% is packed No. 1 container into, under 80～90 ℃ temperature, at the uniform velocity stirred 1 hour;

(4) in No. 2 containers, add the sodium aluminate dissolving to clarification, pour into fast then in No. 1 container, under 30 ℃～40 ℃ temperature, stirred 30 minutes, form gel, place baking oven or thermostatical oil bath, seal, then crystallization 3.5 hours under 90～100 ℃ temperature, crystallization finishes, and is cooled to room temperature;

(5) the crystalline solid product is made solid-liquid separation by filtration, with deionized water solid product is washed PH less than 9, put into baking oven and carry out drying under 80～110 ℃ of temperature, the time surpasses 12 hours, promptly gets A type molecular sieve.

Perhaps:

(1) iron-holder being pulverized at the attapulgite clay below 5%, crossed 120 mesh sieves, is to mix at 1: 1.2 with yellow soda ash with mass ratio, puts into high-temperature roasting device and carry out roasting under 800 ℃ temperature, time remaining 1 hour;

(2) sodium aluminate is dissolved in water, under 30 ℃～40 ℃ temperature, stirred 30 minutes;

(3) material after the roasting is packed in the container, add sodium aluminate solution, under 60 ℃ of temperature, stir, form gel, place baking oven or thermostatical oil bath, seal, be warming up to 90 ℃～100 ℃ then and carry out crystallization, time remaining 6～8 hours;

(4) after reaction finishes, the crystalline solid product being made solid-liquid separation by filtration, is till 7～8 with distilled water wash to pH, puts into baking oven and carry out drying under 80～110 ℃ of temperature, promptly gets A type molecular sieve.

Embodiment

Be explanation specific embodiments of the invention into below, it is synthetic and make it to be converted into amorphous substance with high-temperature roasting to be divided into hydro-thermal, carries out the synthetic two portions of hydro-thermal again.

Embodiment 1-1:

(1) select for use or iron content at the attapulgite clay below 5%;

(2) Na in molar ratio ₂O: Al ₂O ₃: SiO ₂: H ₂O is 3: 1: 2: the above-mentioned attapulgite clay of 185 apolegamys, it is joined in the NaOH solution of 3L4mol/L, and stirs 10～20 minutes to all dissolving, solution all is placed in two containers, be denoted as No. 1 container, No. 2 containers;

(3) with the 125g iron-holder in the attapulgite clay below 5% is packed No. 1 container into, under 80～90 ℃ temperature, at the uniform velocity stirred 1 hour;

(4) in No. 2 containers, add the dissolving of 117g sodium aluminate to clarification, pour into fast then in No. 1 container, under 30 ℃ of temperature, stirred 30 minutes, form gel, place baking oven or thermostatical oil bath, seal, crystallization 3.5 hours under 90 ℃ temperature then, crystallization finishes, and is cooled to room temperature;

(5) the crystalline solid product is made solid-liquid separation by filtration, with deionized water solid product is washed PH less than 9, put into baking oven and carry out drying under 80 ℃ of temperature, the time surpasses 12 hours, promptly gets A type molecular sieve.

Embodiment 1-2:

(1) select for use or iron content at the attapulgite clay below 5%, Na in molar ratio ₂O: Al ₂O ₃: SiO ₂: H ₂O is 3: 1: 2: the above-mentioned attapulgite clay of 185 apolegamys, it is joined in the NaOH solution of 1.5L4mol/L, and stirs 10～20 minutes to all dissolving, solution all is placed in two containers, be denoted as No. 1 container, No. 2 containers;

(2) with the 125g iron-holder in the attapulgite clay below 5% is packed No. 1 container into, under 90 ℃ temperature, at the uniform velocity stirred 1 hour;

(3) in No. 2 containers, add 58.5g and separate, pour into fast then in No. 1 container, under 40 ℃ of temperature, stirred 30 minutes to clarification, form gel, place baking oven or thermostatical oil bath, seal, crystallization 3.5 hours under 100 ℃ temperature then, crystallization finishes, and is cooled to room temperature;

(4) the crystalline solid product is made solid-liquid separation by filtration, with deionized water solid product is washed PH less than 9, put into baking oven and carry out drying under 110 ℃ of temperature, the time surpasses 12 hours, promptly gets A type molecular sieve.

Embodiment 2-1:

(1) select for use or iron content at the attapulgite clay below 5%, Na in molar ratio ₂O: Al ₂O ₃: SiO ₂: H ₂O is 3: 1: 2: the above-mentioned attapulgite clay of 185 apolegamys, and concrete component is: contain Si42.1%; Al6.2%; Ca35%; Fe5.68% with its pulverizing, crosses 120 mesh sieves, and 200 gram attapulgite clays are mixed with 240 gram yellow soda ash, puts into muffle furnace and carry out roasting under 800 ℃ temperature, time remaining 1 hour;

(2) sodium aluminate with 300 grams dissolves in water, stirs 30 minutes under 40 ℃ temperature;

(3) material after the roasting is packed in the container, add sodium aluminate solution, under 60 ℃ temperature, stir, form gel, place baking oven, seal, be warming up to then and carry out crystallization under 90 ℃, time remaining 6 hours;

(4) after reaction finishes, the crystalline solid product being made solid-liquid separation by filtration, is till 7 with distilled water wash to pH, puts into baking oven and carry out drying under 80 ℃ temperature, and the time promptly got A type molecular sieve above 12 hours.

Embodiment 2-2:

(1) select for use or iron content at the attapulgite clay below 5%, Na in molar ratio ₂O: Al ₂O ₃: SiO ₂: H ₂O is 3: 1: 2: the above-mentioned attapulgite clay of 185 apolegamys, and concrete component is: contain Si 51.8%; Al 16.0%; Ca 1.585%; Fe 5.46%, with its pulverizing, crosses 120 orders, and 200 gram attapulgite clays are mixed with 240 gram yellow soda ash, puts into muffle furnace 800 ℃ of following roastings 1 hour.

(2) sodium aluminate with 162 grams dissolves in a spot of water, stirs 30 minutes down at 40 ℃;

(3) material after the roasting is packed in the container, adds the sodium aluminate solution after the dissolving, stirs under 60 ℃ temperature, forms gel, places the thermostatical oil bath, seals, and is warming up to then under 100 ℃ the temperature to carry out crystallization, time remaining 8 hours;

(4) after reaction finishes, the crystalline solid product being made solid-liquid separation by filtration, is till 8 with distilled water wash to pH, puts into baking oven and carry out drying under 110 ℃ temperature, and the time promptly got A type molecular sieve above 12 hours.

Claims (1)

1. adopt the method for the synthetic A type molecular sieve of attapulgite clay, the steps include:

(1) select for use or iron content at the attapulgite clay below 5%, silicone content is 40～70% in its attapulgite clay ore deposit, the content of aluminium is 6～18%; Selecting content for use is sodium aluminate more than 95%, and content is the sodium hydroxide more than 95%;

(2) Na in molar ratio ₂O: Al ₂O ₃: SiO ₂: H ₂O is 3: 1: 2: the above-mentioned attapulgite clay of 185 apolegamys, it is joined in the NaOH solution of 4mol/L, and stirs 10～20 minutes to all dissolving, solution all is placed in two containers, be denoted as No. 1 container, No. 2 containers;

(3) with iron-holder in the attapulgite clay below 5% is packed No. 1 container into, under 80～90 ℃ temperature, at the uniform velocity stirred 1 hour;

(4) in No. 2 containers, add the sodium aluminate dissolving to clarification, pour into fast then in No. 1 container, under 30 ℃～40 ℃ temperature, stirred 30 minutes, form gel, place baking oven or thermostatical oil bath, seal, then crystallization 3.5 hours under 90～100 ℃ temperature, crystallization finishes, and is cooled to room temperature;

(5) the crystalline solid product is made solid-liquid separation by filtration, with deionized water solid product is washed PH less than 9, put into baking oven and carry out drying under 80～110 ℃ of temperature, the time surpasses 12 hours, promptly gets A type molecular sieve.

Perhaps:

(1) iron-holder being pulverized at the attapulgite clay below 5%, crossed 120 mesh sieves, is to mix at 1: 1.2 with yellow soda ash with mass ratio, puts into high-temperature roasting device and carry out roasting under 800 ℃ temperature, time remaining 1 hour;

(2) sodium aluminate is dissolved in water, under 30 ℃～40 ℃ temperature, stirred 30 minutes;

(3) material after the roasting is packed in the container, add sodium aluminate solution, under 60 ℃ of temperature, stir, form gel, place baking oven or thermostatical oil bath, seal, be warming up to 90 ℃～100 ℃ then and carry out crystallization, time remaining 6～8 hours;

(4) after reaction finishes, the crystalline solid product being made solid-liquid separation by filtration, is till 7～8 with distilled water wash to pH, puts into baking oven and carry out drying under 80～110 ℃ of temperature, promptly gets A type molecular sieve.