CN110627088A - Recycling method of low-silicon X molecular sieve synthesis mother liquor - Google Patents

Recycling method of low-silicon X molecular sieve synthesis mother liquor Download PDF

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CN110627088A
CN110627088A CN201810644882.3A CN201810644882A CN110627088A CN 110627088 A CN110627088 A CN 110627088A CN 201810644882 A CN201810644882 A CN 201810644882A CN 110627088 A CN110627088 A CN 110627088A
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source
silicon
mother liquor
molecular sieve
low
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白长敏
徐云鹏
刘中民
刘广业
袁丹华
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Dalian Institute of Chemical Physics of CAS
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Dalian Institute of Chemical Physics of CAS
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
    • C01B39/20—Faujasite type, e.g. type X or Y
    • C01B39/22—Type X
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/90—Other properties not specified above

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  • Chemical Kinetics & Catalysis (AREA)
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  • Inorganic Chemistry (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Abstract

The application discloses a full recycling method of a low-silicon X molecular sieve synthesis mother liquor, which comprises the steps of separating a product from the mother liquor in the molecular sieve preparation process, supplementing an aluminum source, a potassium source and a sodium source into the mother liquor, and recycling. The mother liquor generated by synthesizing the low-silicon molecular sieve by adopting the method is recycled, so that the raw material cost can be fully saved, and the method has economic significance; in the process of recycling the mother liquor, no synthetic waste liquor is discharged, the method is environment-friendly, the cost for treating the waste liquor is saved, and the method has economic and environment-friendly significance when the mother liquor is used once.

Description

Recycling method of low-silicon X molecular sieve synthesis mother liquor
Technical Field
The application relates to a recycling method of a low-silicon X molecular sieve synthesis mother solution, belonging to the field of inorganic chemistry and material chemistry.
Background
The low-silicon X molecular sieve has wide application in the field of pressure swing adsorption oxygen generation, is also widely applied to industries such as petrochemical industry, medicine, agriculture, building, automobile and the like as an adsorbent, and is also widely used as a washing assistant for water softening in the washing industry. The laboratory synthesis method of the low-silicon molecular sieve generally comprises a hydrothermal synthesis method andthe solid-phase synthesis method and the hydrothermal synthesis have the characteristic of uniform mass and heat transfer, the high-purity-phase low-silicon molecular sieve is easy to obtain, and the adsorption capacity and the ion exchange capacity are higher, so that the hydrothermal synthesis has higher application value and can be widely applied to large-scale production. However, the yield of the low-silicon molecular sieve obtained by the hydrothermal synthesis method is low, the product yield is 10-13% calculated by the total feeding amount, a large amount of waste liquid, namely mother liquid, is generated in the production process, and the mother liquid contains unused Na2O、K2O、Al2O3、SiO2If the mother liquor is directly discharged, the loss of raw materials and the environmental pollution are inevitably caused, so how to effectively utilize the mother liquor is a key point and a difficult point in the molecular sieve synthesis industry.
CN1406868A discloses a hydrothermal synthesis method of a low-silicon molecular sieve, which utilizes waste residue or mother liquor of a catalyst plant as part of raw materials for synthesis to synthesize the low-silicon molecular sieve, but the synthesis process also has the problem of generating a large amount of waste liquid.
CN104174356A discloses a method for preparing a low-silicon molecular sieve, but a guiding agent needs to be prepared in the synthesis process, in the mentioned mother liquor utilization scheme, the mother liquor needs to be collected and stored, and the mother liquor is concentrated and processed for reuse, in the production process, fresh deionized water needs to be added while water in the mother liquor is evaporated, and the problems of more processes, more equipment, high energy consumption and long production process exist.
The method focuses on self recycling, and the mother liquor obtained after the low-silicon molecular sieve is synthesized by using fresh raw materials is completely and directly used in the next synthesis without any treatment, so that the discharged or stored mother liquor is not generated in the recycling process, and fresh deionized water is not required to be added, and a guiding agent is not required to be prepared, so that the method has double meanings of economy and environmental protection.
Disclosure of Invention
According to one aspect of the application, a method for recycling a low-silicon X molecular sieve synthesis mother liquor is provided, which is characterized by comprising the following steps:
1) mixing an aluminum source, a sodium source, a potassium source and water to obtain a solution A0; mixing a silicon source and water to obtain a solution B0; adding B0 into A0, aging and crystallizing the obtained mixture C0, and separating to obtain the low-silicon X molecular sieve and a mother solution (the serial number "0" indicates that all fresh raw materials are adopted in the formula, and no mother solution component is added);
2) quantitatively detecting components in the mother liquor by adopting an ion chromatography external standard method;
3) according to the detection result of the step 2), additionally adding An aluminum source, a sodium source and a potassium source into the mother liquor subjected to quantitative detection to obtain a mixture An; mixing a silicon source and water to obtain a solution Bn, adding the Bn into An, aging and crystallizing the obtained mixture Cn, and separating to obtain a low-silicon X molecular sieve and a mother solution;
4) and (3) repeatedly repeating the steps 2) to 3), thereby realizing the recycling of the mother liquor in the synthesis of the low-silicon X molecular sieve.
In the method, the raw materials necessary for producing the molecular sieve product are added into the mother liquor, so that the mother liquor is reused, and all the mother liquor is recycled, so that the production cost is greatly reduced, and the problem of waste liquor discharge is solved.
Preferably, in the mixture C0 in step 1), the molar ratio of the sodium source, the potassium source, the aluminum source, the silicon source and the water is:
Na2O(2.0～6.0)：K2O(1.0～4.0):Al2O3(1.0～2.5):SiO2(0.5～2.0):H2O(80～150)；
wherein the mole number of the sodium source is Na2The mole number of O; the mole number of the potassium source is K2The mole number of O; the mole number of the aluminum source is Al2O3In terms of moles; the mole number of the silicon source is SiO2In terms of moles; the mole number of the water is H2And the mole number of O.
Preferably, in the mixture Cn of the step 3), the molar ratio of the sodium source, the potassium source, the aluminum source, the silicon source and the water is as follows:
Na2O(2.0～6.0)：K2O(1.0～4.0):Al2O3(1.0～2.5):SiO2(0.5～2.0):H2O(80～150)；
wherein the mole number of the sodium source is Na2The mole number of O; the mole number of the potassium source is K2The mole number of O; the mole number of the aluminum source is Al2O3In terms of moles; the mole number of the silicon source is SiO2In terms of moles; the mole number of the water is H2And the mole number of O.
Preferably, the aging in the step 1) and the step 3) is performed for 6-10 hours at the temperature of 55-70 ℃.
Preferably, the crystallization in the step 1) and the step 3) is performed for 5-9 hours at the temperature of 100-110 ℃.
Preferably, the ion chromatography external standard method uses methanesulfonic acid as an eluent, detects the ion concentration in the mother liquor based on the response relation between the ion conductivity peak area and the ion concentration, and converts the mass fraction of each component in the mother liquor by using the ion concentration.
Preferably, the leacheate is 26mmol/L methanesulfonic acid.
Preferably, the sodium source is selected from at least one of sodium sulfate, sodium nitrate, and sodium hydroxide;
the potassium source is at least one of potassium sulfate, potassium nitrate and potassium hydroxide;
the silicon source is at least one of silica sol, sodium silicate and potassium silicate;
the aluminum source is at least one selected from pseudo-boehmite, alumina, sodium aluminate, potassium aluminum sulfate and potassium aluminate.
Preferably, 250mmHg of CO at 25 deg.C2Under air pressure, the low-silicon X molecular sieve is used for CO2Has an adsorption capacity of more than 100cm3/g。
Preferably, 250mmHg of CO at 25 deg.C2Under air pressure, the low-silicon X molecular sieve is used for CO2Has an adsorption capacity of 100cm3/g～120cm3/g。
The beneficial effects that this application can produce include:
1) the mother liquor generated by synthesizing the low-silicon molecular sieve is recycled, so that the raw material cost can be fully saved, and the method has economic significance;
2) in the process of recycling the mother liquor, new deionized water is not needed to be added, no synthetic waste liquor is stored and discharged, the method is environment-friendly, the cost of the deionized water and equipment is saved, the cost of waste liquor treatment is saved, and the method has economic and environment-friendly significance when the mother liquor is used once.
3) The method for synthesizing the low-silicon molecular sieve by adopting the hydro-thermal method has the characteristics of uniform heat and mass transfer, easy obtainment of high-purity phase products and good adsorption performance of the products, and is suitable for large-scale industrial production.
Drawings
FIG. 1 is a scanning electron micrograph of a low silicon X molecular sieve product M0.
FIG. 2 is a scanning electron micrograph of low silicon X molecular sieve product M1.
FIG. 3 is a scanning electron micrograph of low silicon X molecular sieve product M2.
FIG. 4 is a scanning electron micrograph of low silicon X molecular sieve product M3.
FIG. 5 is a scanning electron micrograph of low silicon X molecular sieve product M4.
FIG. 6 is a scanning electron micrograph of low silicon X molecular sieve product M5.
FIG. 7 is a comparison of XRD patterns of low-silicon X molecular sieves synthesized by mother liquor circulation.
FIG. 8 is a comparison of adsorption performance of low-silicon X molecular sieves synthesized by mother liquor circulation.
M0 is a low-silicon molecular sieve product produced by first-pass synthesis under the condition that no mother liquor exists in the formula; m1 is a low-silicon molecular sieve product produced by reformulating all mother liquor obtained by synthesizing M0, namely, the first mother liquor, M2 is a low-silicon molecular sieve product produced by reformulating all mother liquor obtained by synthesizing M1, namely, the second mother liquor, and the like.
Detailed Description
The present application will be described in detail with reference to examples, but the present application is not limited to these examples.
Unless otherwise specified, the raw materials in the examples of the present application were purchased commercially, and the equipment used was the manufacturer's recommended parameters.
In the embodiment, the apparatus for quantitative detection of components is a Dionex ICS-3000 multifunctional ion chromatograph; the detection method is an external standard quantitative method.
Example 1
Weighing 8.3 g of industrial-grade aluminum oxide in a reaction kettle, adding 41.6 g of 30% sodium hydroxide solution, adding 5.5 g of potassium hydroxide, adding 20.1 g of deionized water, stirring uniformly, and dissolving at 140 ℃ to obtain solution A0; 8.0 g of deionized water was added to 16.0 g of water glass to obtain solution B0; slowly adding B0 into A0 under stirring, placing the obtained gel in an oven, aging at 70 ℃ for 8 hours, crystallizing at 100 ℃ for 6 hours, taking out the gel from the reaction kettle, filtering to obtain mother liquor MY1, washing the filter cake, and drying to obtain a product M0.
The method comprises the steps of quantitatively detecting components of MY1 in the mother liquor by adopting an ion chromatography external standard method, detecting the ion concentration of related substances in the mother liquor by using 26mmol/L methanesulfonic acid as eluent according to the response relation between the ion conductivity peak area and the ion concentration, converting the mass fraction of residual substances in the mother liquor by using the ion concentration, and reformulating according to the composition of the residual substances in the mother liquor.
Weighing 7.8 g of industrial-grade aluminum oxide in a reaction kettle, adding all mother liquor MY1 obtained by filtering, adding 2.0 g of potassium hydroxide, uniformly stirring, and dissolving at 140 ℃ to obtain solution A1; 8.0 g of deionized water was added to 16.0 g of water glass to obtain solution B1; slowly adding B1 into A1 under stirring, placing the obtained gel in an oven, aging at 60 ℃ for 10 hours, crystallizing at 100 ℃ for 8 hours, taking out the gel from the reaction kettle, filtering to obtain mother liquor MY2, washing the filter cake, and drying to obtain a product M1.
The components of MY2 were quantitatively determined as described above.
Weighing 7.5 g of industrial-grade aluminum oxide in a reaction kettle, adding all mother liquor MY2 obtained by filtering, adding 2.0 g of potassium hydroxide, adding 3.2 g of 30% sodium hydroxide solution, stirring uniformly, and dissolving at 140 ℃ to obtain solution A2; 8.0 g of deionized water was added to 16.0 g of water glass to obtain solution B2; slowly adding B2 into A2 under stirring, placing the obtained gel in an oven, aging at 65 ℃ for 8 hours, crystallizing at 100 ℃ for 5.5 hours, taking out the reaction kettle, and filtering to obtain mother liquor MY 3; and washing and drying the filter cake to obtain a product M2.
The components of MY3 were quantitatively determined as described above.
Weighing 7.2 grams of industrial-grade aluminum oxide in a reaction kettle, adding all mother liquor MY3 obtained by filtering, adding 2.0 grams of potassium hydroxide, adding 5.4 grams of 30% sodium hydroxide solution, stirring uniformly, and dissolving at 140 ℃ to obtain solution A3; 8.0 g of deionized water was added to 16.0 g of water glass to obtain solution B3; slowly adding B3 into A3 under stirring, placing the obtained gel in an oven, aging at 60 ℃ for 9 hours, crystallizing at 100 ℃ for 6 hours, taking out the gel from the reaction kettle, filtering to obtain mother liquor MY4, washing the filter cake, and drying to obtain a product M3.
The components of MY4 were quantitatively determined as described above.
Weighing 7.2 g of industrial-grade aluminum oxide in a reaction kettle, adding all mother liquor MY4 obtained by filtering, adding 2.1 g of potassium hydroxide, adding 5.0 g of 30% sodium hydroxide solution, uniformly stirring, and dissolving at 140 ℃ to obtain solution A4; 8.0 g of deionized water was added to 16.0 g of water glass to obtain solution B4; slowly adding B4 into A4 under stirring, placing the obtained gel in an oven, aging at 60 ℃ for 8 hours, crystallizing at 100 ℃ for 6.5 hours, taking out the reaction kettle, filtering to obtain mother liquor MY5, washing the filter cake, and drying to obtain a product M4.
The components of MY5 were quantitatively determined as described above.
Weighing 7.1 g of industrial-grade aluminum oxide in a reaction kettle, adding all mother liquor MY5 obtained by filtering, adding 2.2 g of potassium hydroxide, adding 8.0 g of 30% sodium hydroxide solution, stirring uniformly, and dissolving at 140 ℃ to obtain solution A5; 8.0 g of deionized water was added to 16.0 g of water glass to obtain solution B5; slowly adding B5 into A5 under stirring, placing the obtained gel in an oven, aging at 55 ℃ for 10 hours, crystallizing at 100 ℃ for 7 hours, taking out the gel from the reaction kettle, filtering to obtain mother liquor MY6, washing and drying the filter cake to obtain a product M5.
Example 2 sample morphology analysis
The results of the sample morphology analysis of M0-M5 are shown in FIGS. 1-6.
The instrument for carrying out the morphology analysis is a Hitachi TM 3000 desktop scanning electron microscope with an accelerating voltage of 15 kV;
as can be seen from FIGS. 1 to 6, the crystal shape of the sample was stable and no mixed crystal existed.
Example 3 sample phase analysis
The results of the crystal phase analysis of M0-M5 are shown in FIG. 7.
The apparatus used for the analysis of the crystalline phase was an X-ray diffractometer model PANalytical X' Pert PRO, a Cu target, a Kalpha radiation source (lambda 0.15418nm), a voltage of 40kV, a current of 40mA, a scanning range of 5-60 DEG；；
As can be seen from FIG. 7, the XRD spectra of the molecular sieve synthesized by mother liquor circulation and the molecular sieve synthesized by new raw material are basically the same, and both can obtain the low-silicon molecular sieve product with high purity phase
Example 4 analysis of carbon dioxide adsorption Properties of samples
And (3) analyzing the carbon dioxide adsorption performance of M0-M5.
The instrument for analyzing the carbon dioxide adsorption performance is a micromeritics SAP 2020 type physical adsorption instrument, a sample is subjected to vacuum-pumping heating pretreatment for 4 hours at 350 ℃, the free volume of the sample tube is measured by taking He as a medium, carbon dioxide is taken as an adsorption gas, and physical adsorption measurement is carried out at 25 ℃ and 1.9-300 mmHg.
As can be seen from FIG. 8, the amount of carbon dioxide adsorbed by the products M0-M5 remained substantially unchanged at different pressures. Therefore, the mother solution is circularly synthesized, so that the raw material cost is saved and the pollution to the environment is reduced on the premise of ensuring the synthesis effect.
Although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.

Claims (10)

1. A recycling method of low-silicon X molecular sieve synthesis mother liquor is characterized by comprising the following steps:
1) mixing an aluminum source, a sodium source, a potassium source and water to obtain a solution A0; mixing a silicon source and water to obtain a solution B0; adding B0 into A0, aging and crystallizing the obtained mixture C0, and separating to obtain low-silicon X molecular sieve and mother liquid (the serial number "0" indicates that all fresh raw materials are adopted in the formula, and no mother liquid component is added);
2) quantitatively detecting components in the mother liquor by adopting an ion chromatography external standard method;
3) according to the detection result of the step 2), additionally adding An aluminum source, a sodium source and a potassium source into the mother liquor subjected to quantitative detection to obtain a mixture An; mixing a silicon source and water to obtain a solution Bn, adding the Bn into An, aging and crystallizing the obtained mixture Cn, and separating to obtain a low-silicon X molecular sieve and a mother solution;
4) and (3) repeatedly repeating the steps 2) to 3), thereby realizing the recycling of the mother liquor in the synthesis of the low-silicon X molecular sieve.
2. The method for recycling a mother liquor for synthesizing a low-silicon X molecular sieve as claimed in claim 1, wherein in the mixture C0 of the step 1), the molar ratio of the sodium source, the potassium source, the aluminum source, the silicon source and the water is as follows:
Na2O(2.0～6.0)：K2O(1.0～4.0):Al2O3(1.0～2.5):SiO2(0.5～2.0):H2O(80～150)；
wherein the mole number of the sodium source is Na2The mole number of O; the mole number of the potassium source is K2The mole number of O; the mole number of the aluminum source is Al2O3In terms of moles; the mole number of the silicon source is SiO2In terms of moles; the mole number of the water is H2And the mole number of O.
3. The method for recycling a mother liquor for synthesizing a low-silicon X molecular sieve as claimed in claim 1, wherein in the mixture Cn of the step 3), the molar ratio of the sodium source, the potassium source, the aluminum source, the silicon source and the water is as follows:
Na2O(2.0～6.0)：K2O(1.0～4.0):Al2O3(1.0～2.5):SiO2(0.5～2.0):H2O(80～150)；
wherein the mole number of the sodium source is Na2The mole number of O; the mole number of the potassium source is K2The mole number of O; the mole number of the aluminum source is Al2O3In terms of moles; the mole number of the silicon source is SiO2In terms of moles; the mole number of the water is H2And the mole number of O.
4. The recycling method of the low-silicon X molecular sieve synthesis mother liquor according to claim 1, wherein the aging in the step 1) and the step 3) is performed for 6-10 hours at 55-70 ℃.
5. The recycling method of the low-silicon X molecular sieve synthesis mother liquor according to claim 1, wherein the crystallization in the step 1) and the step 3) is performed at 100-110 ℃ for 5-9 h.
6. The method of claim 1, wherein the ion chromatography external standard method comprises detecting the ion concentration of the mother liquor by using methanesulfonic acid as an eluent and based on the response relationship between the ion conductivity peak area and the ion concentration, and converting the mass fraction of each component in the mother liquor by using the ion concentration.
7. The method for recycling a mother liquor for synthesizing a low-silicon X molecular sieve according to claim 6, wherein the leacheate is 26mmol/L methanesulfonic acid.
8. The method for recycling a mother liquor for synthesizing a low-silicon X molecular sieve according to claim 1, wherein the sodium source is at least one selected from sodium sulfate, sodium nitrate and sodium hydroxide;
the potassium source is at least one of potassium sulfate, potassium nitrate and potassium hydroxide;
the silicon source is at least one of silica sol, sodium silicate and potassium silicate;
the aluminum source is at least one selected from pseudo-boehmite, alumina, sodium aluminate, potassium aluminum sulfate and potassium aluminate.
9. The method of claim 1, wherein the CO at 25 ℃ and 250mmHg is recycled2Under air pressure, the low-silicon X molecular sieve is used for CO2Has an adsorption capacity of more than 100cm3/g。
10. The method of claim 1, wherein the CO at 25 ℃ and 250mmHg is recycled2Under air pressure, the low-silicon X molecular sieve is used for CO2Has an adsorption capacity of 100cm3/g～120cm3/g。
CN201810644882.3A 2018-06-21 2018-06-21 Recycling method of low-silicon X molecular sieve synthesis mother liquor Pending CN110627088A (en)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3906076A (en) * 1973-10-03 1975-09-16 Grace W R & Co Process for producing zeolite X molecular sieve bodies
CN1406868A (en) * 2001-08-29 2003-04-02 中国石油化工股份有限公司 X zeolite preparation
CN102225772A (en) * 2011-04-15 2011-10-26 大连理工大学 Method for utilizing molecular sieve systhesis mother liquor
CN102502687A (en) * 2011-10-18 2012-06-20 大连理工大学 Method for greenly synthesizing Ti-Si molecular sieve
CN104174356A (en) * 2014-08-20 2014-12-03 洛阳市建龙化工有限公司 Preparation method of potassium-free low-aluminum-silicon-ratio X-type molecular sieve adsorbent
CN106745044A (en) * 2017-02-24 2017-05-31 太原理工大学 One kind uses Na2CO3The method for aiding in synthesizing low silicon aluminum ratio X-type molecular sieve

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3906076A (en) * 1973-10-03 1975-09-16 Grace W R & Co Process for producing zeolite X molecular sieve bodies
CN1406868A (en) * 2001-08-29 2003-04-02 中国石油化工股份有限公司 X zeolite preparation
CN102225772A (en) * 2011-04-15 2011-10-26 大连理工大学 Method for utilizing molecular sieve systhesis mother liquor
CN102502687A (en) * 2011-10-18 2012-06-20 大连理工大学 Method for greenly synthesizing Ti-Si molecular sieve
CN104174356A (en) * 2014-08-20 2014-12-03 洛阳市建龙化工有限公司 Preparation method of potassium-free low-aluminum-silicon-ratio X-type molecular sieve adsorbent
CN106745044A (en) * 2017-02-24 2017-05-31 太原理工大学 One kind uses Na2CO3The method for aiding in synthesizing low silicon aluminum ratio X-type molecular sieve

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