CN1613762A

CN1613762A - Method for preparing molecular sieve by alkaline slag and potash feldspar

Info

Publication number: CN1613762A
Application number: CN 200310113952
Authority: CN
Inventors: 乔希海
Original assignee: Individual
Current assignee: Individual
Priority date: 2003-11-06
Filing date: 2003-11-06
Publication date: 2005-05-11

Abstract

A production of molecular screen by caustic sludge and potash feldspar is disclosed. It is carried out by proportioning, roasting, breaking, crystallizing, washing, filtering and drying to obtain molecular screen powder and magnetic chloride, potassium chloride and sodium chloride etc. products. It advantages include full utilization, low cost and no waste discharge.

Description

The method of alkaline residue, potassium felspar sand system molecular sieve

The present invention relates to utilize the method for ammonia alkali waste residue and potassium felspar sand system molecular sieve.

Alkaline residue is that the waste material that discharges in the soda ash process is produced in solvay soda process, do not pile up all the year round and utilize, more to the comprehensive utilizating research achievement of waste residue in recent years, as pilot scale stage achievement alkaline residue system cement, alkaline residue system calcium silicate fertilizer etc., utilize the patent of alkaline residue making engineering soil using also to authorize already, patent ZL99123761.7 is the processing method with alkaline residue and potassium felspar sand system Repone K, this technology is to make the Repone K fertilizer that China is badly in need of with waste soda residue and potassium felspar sand, in preparation process, obtained the superfine solid materials of a large amount of particles, by analysis, SiO in this material ₂, Al ₂O ₃Ratio is suitable for further research and development and makes molecular sieve, and the research that therefore fully utilizes alkaline residue, potassium felspar sand exploitation high value added product manufacturing molecular sieve becomes the task of top priority.

The object of the invention provides the method for a kind of alkaline residue, potassium felspar sand system molecular sieve, and this programme both can obtain the zeolite product of high added value, and Repone K fertilizer that can obtain being badly in need of again and magnetic oxygenated iron product are the good schemes that makes full use of alkaline residue and potassium felspar sand raw material.

The present invention realizes like this, with reference to Fig. 1, it is to produce the waste residue liquid of alkaline residue that the waste residue liquid that discharges in the soda ash process piles up all the year round or directly discharging through stiff with solvay soda process, wet slag after the press filtration or waste residue liquid are through pre-carbonization, wet slag after the press filtration is one of raw material, the potassium felspar sand raw material is through fragmentation, levigate, magnetic separation extracts martial ethiops, obtain containing potassium felspar sand＞95%, the potassium felspar sand fine ore of TFeO＜1% is as two of raw material, this is that the method for feedstock production molecular sieve adopts following step to carry out with alkaline residue and potassium felspar sand fine ore: with alkaline residue (1) and potassium felspar sand fine ore (2) with potassium felspar sand: the ratio adding charge pulp preparation process (3) of alkaline residue=1: 0.5～5, add calcium chloride solution (4) again, material enters calcining process (5) in the charge pulp operation after mixing and stirring, under 750-900 ℃ of temperature condition roasting 35-90 minute, grog after the roasting enters pulverizing process (6), grog after the pulverizing prepares molecular sieve with hydrothermal synthesis method, it is characterized in that:

1) waste residue liquid of alkaline residue that the waste residue liquid that discharges in the solvay soda process soda ash production process is piled up all the year round or directly discharging through wet slag after stiff, the press filtration or waste residue liquid the wet slag after pre-carbonization, press filtration as one of raw material, with levigate potassium felspar sand fine ore behind the extraction martial ethiops as two of raw material;

2) above-mentioned two kinds of raw materials and CaCl ₂Solution is by preparation, roasting, grog after the pulverizing prepares molecular sieve with hydrothermal synthesis method, specific practice is: grog and caustic soda and water are mixed into colloidal by 1: 0.3～0.6: 10～20 parts by weight, this is for becoming glue process (7), leave standstill at ambient temperature then, aging 3-5 hour, under 90～110 ℃ of temperature condition crystallization 4-11 hour afterwards, this is crystallisation process (8), add water washing regulator solution pH value again and be till the 7-11, filter (9) then, solid after the filtration is dry (10) under 105 ℃ of temperature condition, obtain X type molecular sieve powder (11), filtered wash solution extracts Repone K through conventional technology, calcium chloride, the sodium-chlor product;

Another kind of way is: with grog and calcium hydroxide and water by 1: 0.5～0.8: the parts by weight of 10-20 mix into colloidal, leave standstill at ambient temperature then, wore out 3-5 hour, it is under the 90-110 ℃ of condition crystallization 4-11 hour in temperature afterwards, till adding water washing again and transferring the solution pH value to be 7-11, filter then, solid after filtration drying under 105 ℃ of temperature condition obtains the molecular sieve powder, and filtered wash solution extracts Repone K, calcium chloride, sodium-chlor product through conventional technology.

Containing the TFeO amount in the potassium felspar sand of the present invention is about 5%, can extract useful martial ethiops (patent 02131255.9 technology) through broken, levigate, multi-stage magnetic separation, obtain containing potassium felspar sand＞95% after carrying iron, the potassium felspar sand fine ore of TFeO＜1%, after it and alkaline residue batching, the roasting, insoluble K2O is converted into solubility K in the potassium felspar sand more than 80% ₂O, all the other are CaO, SiO ₂, Al ₂O ₃With a spot of MgO, K ₂The Cl of O, trace ^-And SO ₄ ⁼, SiO wherein ₂With Al ₂O ₃Ratio meet the preparation ratio of molecular sieve fully, therefore in this programme except obtaining the molecular sieve powder, also can obtain ferric oxide, Repone K, calcium chloride, sodium-chlor product, become the alkaline residue waste material in the technical solution of the present invention into precious, make that all compositions are fully used in alkaline residue, the potassium felspar sand, therefore this programme economical, societal benefits are remarkable, and three-waste free discharge.

Description of drawings:

Fig. 1 is the flow process simplified schematic diagram of the method for alkaline residue of the present invention, potassium felspar sand system molecular sieve.

Example 1:

200 order potassium felspar sand fine ores and alkaline residue are prepared burden in 1: 2 ratio, add 0.7 part of CaCl of potassium felspar sand weight ₂(with 42%CaCl ₂The solution form adds) in non-hibernating eggs slurry preparation process, enter calcining process after the mixing and stirring, roasting is 90 minutes under 750～900 ℃ of temperature condition, after the discharging static 30 minutes, broken again, grog after the fragmentation and caustic soda and water mix in reactor by 1: 0.4: 15 parts by weight, stir, and in reactor, leave standstill at ambient temperature, aging 4 hours, crystallization 6 hours under 100 ℃ of conditions then, again material is placed on add water washing in the tank and transfer the solution pH value to be 7-11 till, filter then, the solid after the filtration enters moisture eliminator thorough drying under 105 ℃ of conditions, obtain X type molecular sieve powder, filtrate is extracted KCl with common process, CaCl ₂, NaCl do not describe in detail herein.

Example 2:

Batching and roasting, pulverising step are with example 1

Grog and calcium hydroxide and water are by 1: 0.5: 20 parts by weight mixing and stirring and add a small amount of zeolite seed crystal (general chemical product) in reactor, leave standstill at ambient temperature, wore out 5 hours, crystallization 8 hours under 100 ℃ of conditions then, again material is placed on add water washing in the tank and transfer pH value to be 7-11 till, filter then, filter back solid (105 ℃) thorough drying in moisture eliminator and obtain the molecular sieve powder, all the other steps are omitted.

With 10kg potassium felspar sand and 20kg alkaline residue proportioning, by the series of steps preparation, at last can about 8.5kg molecular sieve powder.

Claims

1, a kind of alkaline residue, the method of potassium felspar sand system molecular sieve, it is to produce the waste residue liquid of alkaline residue that the waste residue liquid that discharges in the soda ash process piles up all the year round or directly discharging through stiff with solvay soda process, wet slag after the press filtration or waste residue liquid are through pre-carbonization, wet slag after the press filtration is one of raw material, the potassium felspar sand raw material is through fragmentation, levigate, magnetic separation extracts martial ethiops and obtains containing potassium felspar sand＞95%, the potassium felspar sand fine ore of TFeO＜1% is as two of raw material, this is that the method for feedstock production molecular sieve adopts following step to carry out with alkaline residue and potassium felspar sand fine ore: with alkaline residue (1) and potassium felspar sand fine ore (2) with potassium felspar sand: the ratio adding charge pulp preparation process (3) of alkaline residue=1: 0.5～5, add calcium chloride solution (4) again, material enters calcining process (5) in the charge pulp operation after mixing and stirring, under 750～900 ℃ of temperature condition, roasting 35～90 minutes, grog after the roasting enters pulverizing process (6), grog after the pulverizing prepares molecular sieve with hydrothermal synthesis method, and its feature is as follows:

1) waste residue liquid of solvay soda process being produced alkaline residue that the waste residue liquid that discharges in the soda ash process piles up all the year round or directly discharging through wet slag after stiff, the press filtration or waste residue liquid the wet slag after pre-carbonization, press filtration as one of raw material, with levigate potassium felspar sand fine ore behind the extraction martial ethiops as two of raw material;

2) above-mentioned two kinds of raw materials and calcium chloride solution are by preparation, roasting, grog after the pulverizing prepares molecular sieve with hydrothermal synthesis method, specific practice is: grog and caustic soda and water are mixed into colloidal by 1: 0.3～0.6: 10～20 parts by weight, this is for becoming glue process (7), leave standstill at ambient temperature then, aging 3～5 hours, under 90～110 ℃ of temperature condition crystallization 4-11 hour afterwards, this is crystallisation process (8), add water washing regulator solution pH value again and be till the 7-11, filter (9) then, solid after the filtration is dry (10) under 105 ℃ of temperature condition, obtain X type molecular sieve (11), filtered wash solution (12) extracts Repone K through conventional technology, calcium chloride, the sodium-chlor product;

Another kind of way is: grog and calcium hydroxide and water are carried out stirring and evenly mixing by 1: 0.5～0.8: 10～20 parts by weight become colloidal, leave standstill at ambient temperature then, wore out 3～5 hours, it is under 90～110 ℃ of conditions crystallization 4-11 hour in temperature afterwards, add the thick solution pH value of water washing again and be till the 7-11, filter then, solid after the filtration is the dry molecular sieve powder that gets under 105 ℃ of temperature condition, and filtered wash solution extracts Repone K, calcium chloride, sodium-chlor product through conventional technology.