CN102190312A - Method for recycling molecular sieve mother solution - Google Patents
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- CN102190312A CN102190312A CN 201010128307 CN201010128307A CN102190312A CN 102190312 A CN102190312 A CN 102190312A CN 201010128307 CN201010128307 CN 201010128307 CN 201010128307 A CN201010128307 A CN 201010128307A CN 102190312 A CN102190312 A CN 102190312A
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Abstract
The invention discloses a method for recycling molecular sieve crystallization mother solution, which comprises the following steps of: (1) preparing a material for synthesizing a molecular sieve, gelatinizing, crystallizing, filtering, and collecting all molecular sieve crystallization mother solution; (2) using the obtained all molecular sieve crystallization mother solution for synthesis of the molecular sieve directly, mixing with a solid silicon source, an aluminum source and alkali, and adding or not adding molecular sieve seed crystals and a template agent to obtain a reaction mixture; and (3) crystallizing the obtained reaction mixture according to the conventional hydrothermal method, obtaining a filter cake, namely a molecular sieve product, and filtering and collecting all molecular sieve crystallization mother solution, wherein the obtained all molecular sieve crystallization mother solution can be circularly utilized according to the sequence of steps (2) and (3). In the synthesis of the molecular sieve, alkaline waste liquor is not discharged basically, the total silicon utilization rate is more than or equal to 90 percent, and the yield of the molecular sieve product is over 90 percent.
Description
Technical field
The present invention relates to the molecular sieve synthesis technical field, more particularly, relate to a kind of molecular sieve crystallization mother liquor after utilizing Si-Al molecular sieve synthetic and carry out molecular sieve synthetic recoverying and utilizing method.
Background technology
Molecular sieve is important catalyst or a catalyst activity constituent element in refining of petroleum and the chemical process.Prior art is when the synthesizing Si-Al molecular sieve, silicon-containing compound (water glass, silicon sol and organo-silicon ester etc.), aluminum contained compound (hydrated aluminum oxide, aluminium salt etc.), alkali (sodium hydroxide, potassium hydroxide etc.) and water are mixed by suitable proportion, add or do not add organic formwork agent and in autoclave, heat certain hour, promptly obtain molecular sieve crystal.Under alkaline condition, some silicon can remain in the mother liquor and not be fully used.If the mother liquor after will synthesizing in factory has not only increased the total amount of sewage disposal directly as sewage, also can cause very big waste, reduced the utilization ratio of silicon.Because the big and free silicon-dioxide of silicon content free settling not very easily causes the suspended substance of externally discharged waste water to exceed standard, thereby strengthens the intractability of sewage in the mother liquor; And the Na in the crystallization mother liquor
2The O height has increased the filter residue processing costs.
Usually, the NaY molecular sieve silica alumina ratio that feeds intake when synthetic is generally 8～12, and the silica alumina ratio of product is generally 4.5～5.5.Therefore, the utilization ratio of silicon has only about 60% in the starting material.The research report that also has some to utilize the NaY mother liquor to recycle in the prior art.For example, DD 227416A discloses and has used the mother liquor of synthetic y-type zeolite or mordenite to synthesize X type zeolite; Disclose among SU975573A, CN 1634764 and the CN 1854066 and utilized the NaY mother liquor to prepare silicon (aluminium) glue, and then used the raw material of this silicon (aluminium) glue as synthetic NaY zeolite; CN 1631780 relates to a kind of crystallization mother liquor of the NaY of utilization molecular sieve and the method that sodium aluminate solution is produced the 4A molecular sieve.CN 1057067 discloses the method for a kind of synthetic ZSM-5 of silicon aluminium microsphere of the NaY of use mother liquor preparation.In most cases of the prior art, all need earlier the formation of the silicon in the mother liquor with silica gel or silica-alumina gel to be settled down, prepared silicon (aluminium) gel also needs can be used for the synthetic of molecular sieve after filtration and/or the washing.In addition, CN 1217232 has proposed a kind of method of utilizing the template synthesis of titanium silicon molecular sieve in the molecular sieve mother liquor; CN1500722 discloses template in a kind of MCM-22 of use molecular sieve crystallization mother liquor as the part or all of template of molecular sieve synthetic.
Usually, SiO in the molecular sieve crystallization mother liquor
2Content be 30-70g/L, Na
2O content is 20-45g/L, is equivalent to modulus and is rare water glass of 1.65～2.58.If continue adding moisture more silicon source, aluminium source or template solution in feeding intake in that molecular sieve is synthetic, the water silicon ratio of system is increased, thereby reduced molecular sieve synthetic single-autoclave yield rate.
The invention provides a kind of molecular sieve synthetic novel method, i.e. the recoverying and utilizing method of molecular sieve crystallization mother liquor directly feeds intake whole molecular sieve mother liquors and to carry out, and the molecular sieve mother liquor that obtains in each step of repeated multiple times recycle, has made full use of the OH in the mother liquor
-, silicate and water, the crystallization mother liquor of comprehensive utilization molecular sieve overcomes the defective of prior art, and guarantees to obtain higher single-autoclave yield rate.
Summary of the invention
The purpose of this invention is to provide a kind of recoverying and utilizing method of molecular sieve crystallization mother liquor, comprise the steps:
(1) whole molecular sieve crystallization mother liquors is collected in the material of a kind of synthesis of molecular sieve of preparation, one-tenth glue, crystallization and filtration;
(2) with the whole molecular sieve crystallization mother liquor of step (1) gained, be directly used in the synthetic of molecular sieve without any processing, that is, it is mixed with solid silicon source, aluminium source and alkali, add or do not add molecular sieve crystal seed and template, make reaction mixture;
(3) with the reaction mixture of step (2) gained routinely hydrothermal method carry out crystallization, the filter cake of gained is a zeolite product, filters simultaneously to collect to obtain whole molecular sieve crystallization mother liquors;
Wherein, can be with the whole molecular sieve crystallization mother liquor of step (3) gained, according to the order of step (2), (3), recycled for multiple times.
The recoverying and utilizing method of molecular sieve crystallization mother liquor of the present invention, wherein, molecular sieve is a Si-Al molecular sieve described in the step (1), comprises NaY, ZSM-5, ZSM-11, TS-1, MCM-22, Beta or mordenite.Described preferred molecular sieve is ZSM-5, TS-1, MCM-22 or Beta.Wherein, technology such as the material of synthesis of molecular sieve described in the step (1), one-tenth glue, crystallization, filtration, its preparation condition etc. is known routine techniques, the visible reference of detailed content: Verified Syntheses of ZeoliticMaterials, Ed.By H.Robson, Elsevier, 2001, Amsterdam.
The recoverying and utilizing method of molecular sieve crystallization mother liquor of the present invention, wherein, described in the step (2) all crystallization mother liquors comprise that mother liquor that molecular sieve crystallization after-filtration is collected and molecular sieve filter cake are with a spot of washing resulting water lotion afterwards.Wherein said " a small amount of washing " is meant that water lotion is about mother liquor 10-20 weight percent.The present invention directly recycles whole molecular sieve crystallization mother liquors, thereby makes molecular sieve not have the discharging of silicon and alkali in synthetic.
Described molecular sieve crystallization mother liquor of the present invention without any processing, is directly used in the synthetic of molecular sieve, and this technology is to having had not yet to see report.Wherein, whole crystallization mother liquors can mix in any order with solid silicon source, aluminium source and alkali described in the step (2).Wherein, " molecular sieve crystal seed " described in the step (2) refer to any can acceleration molecular the solid and the colloidal solution of sieve synthetic silicon-aluminum containing, described " template " instructs the organism to certain molecular sieve structure.
The recoverying and utilizing method of molecular sieve crystallization mother liquor of the present invention, wherein, solid silicon source comprises any silicon-containing solid compound or natural mineral described in the step (2), comprises solid silicone, silicon (aluminium) glue, precipitation silica gel, white carbon black, kaolin, polynite.Wherein, solid silicon source described in the step (2) is preferably solid silicone, silicon (aluminium) glue, precipitation silica gel, white carbon black.Made reaction mixture in the step (2) with certain mole proportioning, this mole proportioning and step (1) synthetic mole proportioning can be the same or different, and the requirement that the middle mole of step (2) proportioning meets the target synthesis of molecular sieve gets final product.
The recoverying and utilizing method of molecular sieve crystallization mother liquor of the present invention, wherein, the described molecular sieve of synthetic can be identical or different with the described molecular sieve in the step (1) in step (2) and (3).For example, use the crystallization mother liquor of ZSM-5 molecular sieve can be directly used in the synthetic of Beta, MCM-22 or mercerising equimolecular sieve, the crystallization mother liquor of NaY molecular sieve can be used for the synthetic of ZSM-5 or Beta equimolecular sieve.Embodiments of the invention 4 have illustrated that the crystallization mother liquor of NaY molecular sieve is used for the synthetic of ZSM-5 molecular sieve.
Said conventional hydrothermal method in the method steps provided by the invention (3) is meant and does not add crystallization mother liquor and carry out molecular sieve identical crystallization method when synthetic, is known routine techniques.
The recoverying and utilizing method of molecular sieve crystallization mother liquor of the present invention, its innovation is: the whole crystallization mother liquors after molecular sieve is synthesized, without any processing ground, directly it being fed intake is used for synthesis of molecular sieve, thereby makes molecular sieve not have the discharging of silicon and alkali in synthetic; Utilize the mixture of solid silicon source and crystallization mother liquor as molecular sieve synthetic silicon source again; Particularly, also molecular sieve crystallization mother liquor that filter to collect of recycle has repeatedly repeatedly made full use of the OH-in the mother liquor, silicate and water, synthetically utilizes the crystallization mother liquor of molecular sieve.These technological innovations are not all seen in the prior art as yet has report openly.
The recoverying and utilizing method of molecular sieve crystallization mother liquor of the present invention makes molecular sieve not have the alkaline waste liquor discharging substantially in synthetic, makes the molecular sieve crystallization process not have discharging of waste liquid, the utilization ratio of overall silicon 〉=90%.If any discharging, then silicon oxide and sodium oxide are not used in the mother liquor.During prior art ZSM-5 molecular sieve is synthetic, in crystallization mother liquor, contain the SiO of 15-20 weight percent usually
2, and method of the present invention can all be recycled these crystallization mother liquors synthesis of molecular sieve, after the repeatedly circulation by these crystallization mother liquors, uses the yield of gained zeolite product to be higher than 90%.1 ton of molecular sieve of every production, crystallization process can reduce water 1.5-2.0 ton, saves NaOH consumption about 40%.And the present invention uses silicon and the two kinds of silicon sources of solid silicon source in the mother liquor simultaneously, has guaranteed that molecular sieve synthetic water silicon is than not increasing one by one in the mother liquid recycling process.
Description of drawings
Fig. 1: X-ray diffraction (XRD) the crystalline phase figure for Comparative Examples 1 gained sample is typical ZSM-5 molecular sieve, no stray crystal phase.
Fig. 2: X-ray diffraction (XRD) the crystalline phase figure for embodiment 2 gained samples is typical ZSM-5 molecular sieve, no stray crystal phase.Compare with Comparative Examples 1, relative crystallinity is 102%.
Fig. 3: X-ray diffraction (XRD) the crystalline phase figure for embodiment 5 gained samples is typical B eta molecular sieve, no stray crystal phase.
Embodiment
With the following Examples, the present invention is described further.The present invention is unrestricted in following specific embodiment.
In following each embodiment and each Comparative Examples, the test of molecular sieve relative crystallinity adopts x-ray powder diffraction to measure, and comparative sample is not for using crystallization mother liquor synthetic counter sample; The BET surface-area of sample adopts GB/T 5816-1995 standard method to measure; The chemical industry standard HC/T 2830-1997 of the People's Republic of China (PRC) is adopted in the analysis of silicon oxide and sodium oxide in the mother liquor.
Comparative Examples 1
With 55.0 gram sodium hydroxide, 31.5 gram sodium metaaluminate (chemical reagents corporation of traditional Chinese medicines group, Al
2O
3Content 41 heavy %) be dissolved in 1200 ml waters with 12.5 gram 4-propyl bromides, add 22.8 gram NaY (Chang Ling oil-refining chemical factory catalyst plant) and 500 gram silica gel (Haiyang Chemical Plant, Qingdao successively, the 40-120 order, burning residual solid content is 95%), be transferred to after stirring in 2 liters of autoclaves, in 175 ℃ of following crystallization 24 hours, cooled and filtered, washing and drying, the XRD crystalline phase figure of products obtained therefrom is the ZSM-5 structure as shown in Figure 1, its degree of crystallinity is set at 100%, and the BET surface-area is 324m2/g.Crystallization mother liquor after the filtration is collected and is used for the synthetic of embodiment 1.With respect to solid silicon source, the yield of gained ZSM-5 sieve sample is about 84%.
Embodiment 1
With 790 milliliters of (SiO of the crystallization mother liquor in the Comparative Examples 1
2: 65.0g/L; Na
2O:38.8g/L) mix with 500 ml waters, add 4.7 gram sodium hydroxide, 22.8 gram sodium metaaluminates and 8.8 gram 4-propyl bromide dissolvings, add 360 gram silica gel (Haiyang Chemical Plant, Qingdao, 40-120 orders, burning residual solid content is 95%), be transferred to after stirring in 2 liters of autoclaves, in 175 ℃ of following crystallization 24 hours, cooled and filtered, washing and drying, the XRD crystalline phase figure of products obtained therefrom as shown in Figure 2, be the ZSM-5 structure, its relative crystallinity is 102%, and the BET surface-area is 340m2/g.Crystallization mother liquor after the filtration is collected and is used for the synthetic of embodiment 2.With respect to solid silicon source, the yield of gained ZSM-5 sieve sample is about 92%.
Embodiment 2
With 898 milliliters of (SiO of the crystallization mother liquor among the embodiment 1
2: 46.9g/L; Na
2O:23.5g/L) mix with 300 ml waters, add 14.4 gram sodium hydroxide, 22.8 gram sodium metaaluminates and 8.8 gram 4-propyl bromide dissolvings, add 360 gram silica gel (burning residual solid content is 95% for Haiyang Chemical Plant, Qingdao, 40-120 order), be transferred to after stirring in 2 liters of autoclaves, in 175 ℃ of following crystallization 24 hours, cooled and filtered, washing and drying, the XRD crystalline phase figure of products obtained therefrom is similar to Fig. 2, be the ZSM-5 structure, its relative crystallinity is 105%.Crystallization mother liquor after the filtration is collected and is used for the synthetic of ZSM-5.With respect to solid silicon source, the yield of gained ZSM-5 sieve sample is about 93%.
Embodiment 3
With 820 milliliters of (SiO of the crystallization mother liquor among the embodiment 2
2: 46.0g/L; Na
2O:39.8g/L) mix with 400 ml waters, add 14.4 gram sodium hydroxide, 22.8 gram sodium metaaluminates and 8.8 gram 4-propyl bromide dissolvings, add 360 gram silica gel (burning residual solid content is 95% for Haiyang Chemical Plant, Qingdao, 40-120 order), be transferred to after stirring in 2 liters of autoclaves, in 175 ℃ of following crystallization 24 hours, cooled and filtered, washing and drying, the XRD crystalline phase figure of products obtained therefrom is similar to Fig. 2, be the ZSM-5 structure, its relative crystallinity is 105%.Crystallization mother liquor after the filtration is collected and is used for the synthetic of ZSM-5.With respect to solid silicon source, the yield of gained ZSM-5 sieve sample is about 93%.
Embodiment 4
According to SiO2: Al2O3: Na2O: H2O=9.4: 3.0: 1: the 210 moles of synthetic NaY of proportionings, SiO in the gained NaY crystallization mother liquor
2Be 56.6g/L; Na
2O:24.8g/L.900 milliliters of NaY crystallization mother liquors mix with 300 ml waters, add 13.8 gram sodium hydroxide, 22.8 gram sodium metaaluminates and 8.8 gram 4-propyl bromide dissolvings, add 360 gram silica gel (Haiyang Chemical Plant, Qingdao, the 40-120 order, burning residual solid content is 95%), be transferred to after stirring in 2 liters of autoclaves, in 175 ℃ of following crystallization 24 hours, cooled and filtered, washing and drying, products obtained therefrom are typical ZSM-5 molecular sieve, and its degree of crystallinity is 110%.After collecting, crystallization mother liquor after the filtration can continue on for the synthetic of ZSM-5.Illustrate that the molecular sieve mother liquor can be used for the different structure molecular sieve and synthesize.
Comparative Examples 2
With 3.49 gram sodium hydroxide and 0.953 gram sodium metaaluminate (Al2O3:53.52%, Na2O:40.52%) be dissolved in 50.4 ml waters, add the Beta molecular sieve (Chang Ling oil-refining chemical factory catalyst plant) and 12.0 of 1.20 grams after the roastings successively and restrain fresh sedimentary silica gel, be transferred to after stirring in 100 milliliters of autoclaves, in 145 ℃ of following crystallization 24 hours, cooled and filtered, washing and drying, products obtained therefrom are the BETA molecular sieve of pure phase, and its degree of crystallinity is set at 100%.Crystallization mother liquor after the filtration is collected and is used for the synthetic of embodiment 5.With respect to solid silicon source, the yield of BETA molecular sieve is 30%.
With 30 milliliters of (SiO of the crystallization mother liquor in the Comparative Examples 2
2: 54.2g/L; Na
2O:25.8g/L) mix with 20 ml waters, add 2.72 gram sodium hydroxide and 0.953 gram sodium metaaluminate dissolving, add the Beta molecular sieve after 10.4 gram white carbon blacks and 1.2 restrain roastings, be transferred to after stirring in 100 milliliters of autoclaves, in 145 ℃ of following crystallization 24 hours, cooled and filtered, washing and drying, the XRD crystalline phase figure of products obtained therefrom as shown in Figure 3, be the BETA molecular sieve, its degree of crystallinity is 110%.After collecting, crystallization mother liquor after the filtration can continue on for the synthetic of Beta molecular sieve.With respect to solid silicon source, the yield of BETA molecular sieve is 81%.
Claims (7)
1. the recoverying and utilizing method of a molecular sieve crystallization mother liquor is characterized in that, comprises the steps:
(1) whole molecular sieve crystallization mother liquors is collected in the material of a kind of synthesis of molecular sieve of preparation, one-tenth glue, crystallization and filtration;
(2) the whole molecular sieve crystallization mother liquor of step (1) gained is directly used in the synthetic of molecular sieve, it is mixed with solid silicon source, aluminium source and alkali, add or do not add molecular sieve crystal seed and template, make reaction mixture;
(3) with the reaction mixture of step (2) gained routinely hydrothermal method carry out crystallization, the filter cake of gained is a zeolite product, filters simultaneously to collect to obtain whole molecular sieve crystallization mother liquors;
Wherein, can be with the whole molecular sieve crystallization mother liquor of step (3) gained, according to the order of step (2), (3), recycled for multiple times.
2. recoverying and utilizing method as claimed in claim 1 is characterized in that, molecular sieve is a Si-Al molecular sieve described in the step (1), is NaY, ZSM-5, ZSM-11, TS-1, MCM-22, Beta or mordenite.
3. recoverying and utilizing method as claimed in claim 2 is characterized in that, molecular sieve is ZSM-5, TS-1, MCM-22 or Beta described in the step (1).
4. recoverying and utilizing method as claimed in claim 1 is characterized in that, whole crystallization mother liquors described in the step (2) comprise mother liquor and the molecular sieve filter cake a small amount of washing resulting water lotion afterwards that molecular sieve crystallization after-filtration is collected.
5. recoverying and utilizing method as claimed in claim 1 is characterized in that, solid silicon source comprises any silicon-containing solid compound or natural mineral described in the step (2), is solid silicone, silicon (aluminium) glue, precipitation silica gel, white carbon black, kaolin or polynite.
6. recoverying and utilizing method as claimed in claim 5 is characterized in that, solid silicon source described in the step (2) is solid silicone, silicon (aluminium) glue, precipitation silica gel, white carbon black.
7. recoverying and utilizing method as claimed in claim 1 is characterized in that, the described molecular sieve of synthetic can be identical or different with the described molecular sieve in the step (1) in step (2) and (3).
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