CN103130238A - HMCM-49 molecular sieve production method - Google Patents
HMCM-49 molecular sieve production method Download PDFInfo
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- CN103130238A CN103130238A CN2011103802778A CN201110380277A CN103130238A CN 103130238 A CN103130238 A CN 103130238A CN 2011103802778 A CN2011103802778 A CN 2011103802778A CN 201110380277 A CN201110380277 A CN 201110380277A CN 103130238 A CN103130238 A CN 103130238A
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Abstract
The present invention relates to a HMCM-49 molecular sieve production method, which comprises: adopting silica sol, sodium aluminate or sodium aluminate, hexamethyleneimine, desalted water, hydrogen peroxide and citric acid as raw materials, and carrying out material preparing, gelatinizing and crystallization in a reaction kettle; adopting a plate and frame filter press to separate a mother liquor to be recycled; adding the desalted water to filter cake, adopting hydrogen peroxide to carry out oxidation, cooling, and adopting a 5-20% citric acid aqueous solution to carry out pulping; and adopting a spiral vane type dynamic filter press to carry out washing and exchanging, and carrying out drying and roasting to obtain the HMCM-49 molecular sieve, wherein the liquid portion is subjected to evaporation and condensation to be adopted as the desalted water so as to be recycled. According to the present invention, the wastewater emission amount is 1/20 of the wastewater emission amount of the traditional process, the waste gas emission amount is 1/2-1/3 of the waste gas emission amount of the traditional process, and the solid sodium citrate waste can be used in a degradation manner.
Description
Technical field:
The present invention relates to a kind of HMCM-49 method for producing molecular sieve, exactly relate to the HMCM-49 method for producing molecular sieve that a kind of discharge of wastewater is few, exhaust gas emission is few.
Background technology:
The HMCM-49 molecular sieve is preparation HMCM-49 catalyzer direct material, to carry out plastic and crystallization by silicon sol, sodium aluminate (or sodium metaaluminate) aqueous solution and hexamethylene imine, isolate mother liquor, produce the NaMCM-49 molecular sieve, through the aqueous ammonium nitrate solution exchange, carry out drying and roasting, produce the HMCM-49 molecular sieve.
At present, produce the HMCM-49 molecular sieve, in the process of plastic and crystallization, its reaction is carried out in the aqueous solution, contain a certain amount of unreacted hexamethylene imine and directly enter mother liquor, mother liquor directly discharges as waste water usually, owing to containing the 8-12% hexamethylene imine in mother liquor, hexamethylene imine is expensive on the one hand, and directly discharging increases the molecular sieve production cost; The mother liquor that another side contains hexamethylene imine directly discharges, and causes environmental pollution.In the process of roasting, be generally the template with the molecular sieve endoporus, thermal degradation, the hexamethylene imine thermal degradation becomes oxynitrides and carbonic acid gas, and this step is to produce waste gas generation step in HMCM-49 molecular sieve process, is to produce urgent problem.Go out the NaMCM-49 molecular sieve through baked for producing, through the de-salted water washing, deviate from free alkali (sodium hydroxide), consume a large amount of de-salted waters, afterwards with 8-10% aqueous ammonium nitrate solution exchange 3-4 time, produce a large amount of nitrogenous effluents, these two processes produce a large amount of waste water, are also to produce urgent problem.
Chinese patent 02145237.7 has proposed a kind of preparation method of MCM-49 molecular sieve, with the partial mother liquid circulation, and the remaining hexamethylene imine of recovery part, but do not reclaim hexamethylene imine and the thorough problem that solves the hexamethylene imine waste water straightly discharging fully yet.
Summary of the invention
The HMCM-49 method for producing molecular sieve that provides a kind of waste water, waste gas and waste sludge discharge few is provided the object of the invention, and the method is the mother liquor that will separate after crystallization, fully circulation; With hydrogen peroxide oxidation part hexamethylene imine, reduce the discharging of the waste gas of oxynitride; Sodium citrate aqueous solution is adopted in washing and exchange, has thoroughly effected a radical cure the ammonium nitrogen wastewater generation.The present invention simplifies production unit with batching, plastic, crystallization proceed step by step in same reactor, by adopting the Spiralism type dynamic pressure filter, has simplified production process, has reduced the labour intensity of operation.
The technical solution used in the present invention is as follows:
(1) ratio of mother liquor 50-150kg, the NaMCM-49 molecular sieve 1-5kg of silicon sol 200-300kg, sodium metaaluminate or the sodium aluminate 10-20Kg of mass content 25-30%, hexamethylene imine 20-40kg, de-salted water 60-250kg, recycle is mixed in a reactor, plastic, crystallization;
(2) isolate mother liquor through plate-and-frame filter press, recycle; Filter cake after separation is delivered to oxidation trough, adds the 80-250kg de-salted water, under 60-85 ℃, adds 30-26% hydrogen peroxide 12-50kg, and oxidation 2-10h after filtration, drying and roasting, removes hexamethylene imine;
(3) after cooling, enter pulping tank, add the aqueous citric acid solution of 5-20% mass content, wash continuously and exchange on the Spiralism type dynamic pressure filter, washing time 20-40min, Na in molecular sieve
+ 1Ion-cleaning is below 10ppm; Exchange 30-50min, solid part drying, roasting obtain the HMCM-49 molecular sieve; Liquid portion is through the thin-film evaporator vaporize water, then carries out condensation with the recirculated water cooling condenser, and the de-salted water as batching use recycles.
The waste water that the present invention produces is the oxidation template aqueous solution, and waste gas is that roasting process produces a small amount of oxynitride and oxycarbide, and waste residue is Trisodium Citrate for the solid that obtains from vaporizer.From wastewater discharge, be 1/20th of traditional technology, waste gas is 1/1/2nd～three of traditional technology, the use of can demoting of solid citric acid sodium waste residue.
Batching of the present invention, plastic, crystallization are all carried out in the plastic crystallizing kettle, save material-compound tank and colloid generating kettle, have saved facility investment; The mother liquor that plate-and-frame filter press is separated can be recycled, and has reduced the discharging of waste water.
Embodiment
Embodiment 1
With mother liquor, 11kg sodium metaaluminate or the sodium aluminate of 100kg de-salted water, 110kg, the silicon sol of 250kg mass content 26%, the hexamethylene imine of 35kg and 2kg NaMCM-49 molecular sieve add successively, and fully stir, and prepare burden, plastic and crystallization; Under 40 ℃, enter plate-and-frame filter press and isolate mother liquor.Mother liquor is squeezed into the mother liquor storage tank with the mother liquor pump; Filter cake is delivered to oxidation trough, adds the 90kg de-salted water, under 65 ℃, adds the hydrogen peroxide 15kg of mass content 30%, oxidation 5h; Oxidation is sent into plate-and-frame filter press after finishing, and 80kg filtrate is efflux wastewater; Filter cake is sent baking oven to, under 120 ℃, carries out dry 6h; After drying, under 550 ℃, carry out roasting 8h, produce a small amount of waste gas; After cooling, put into pulping tank, add the aqueous citric acid solution of mass content 8%, deliver to the Spiralism type dynamic pressure filter, washing 20min detects Na
+ 1Ion 5ppm; Exchange 30min, solid is sent baking oven back to, under 120 ℃, dry 8h; , under 550 ℃, roasting 18h obtains HMCM-49; Liquid is with being pumped to thin-film evaporator, at 120 ℃, and flow 20m
3/ h evaporates, and steam is sent into condenser, by the flow of recirculated water, controls 65 ℃ of condensator outlet temperature, analyzes the mass concentration of the zwitterion of water of condensation, reaches and moves back the salt solution index, delivers to the desalination water pot, recycles.
Embodiment 2
With mother liquor, 11Kg sodium metaaluminate or the sodium aluminate of 70kg de-salted water, 150kg, the silicon sol of 250kg mass content 26%.The hexamethylene imine of 35kg and 2kg NaMCM-49 molecular sieve add successively, and fully stir, and prepare burden, plastic and crystallization; Under 60 ℃, enter plate-and-frame filter press and isolate mother liquor, mother liquor is squeezed into the mother liquor storage tank with the mother liquor pump; Filter cake is delivered to oxidation trough, adds the 120kg de-salted water, under 65 ℃, adds the hydrogen peroxide 20kg of mass content 30%, oxidation 4h; Oxidation is sent into plate-and-frame filter press after finishing, and filtrate 100kg is efflux wastewater; Filter cake is sent baking oven to, under 120 ℃, carries out dry 10h; Under 540 ℃, carry out roasting 20h, produce a small amount of waste gas; After cooling, put into pulping tank, add the aqueous citric acid solution of mass content 6%, deliver to the Spiralism type dynamic pressure filter, washing 30min detects Na
+ 1Ion 1ppm; Exchange 20min, solid is sent baking oven back to, under 120 ℃, dry 8h; , under 550 ℃, roasting 16h obtains HMCM-49; Liquid is with being pumped to thin-film evaporator, at 110 ℃, and flow 10m
3/ h evaporates, and steam is sent into condenser, by the flow of recirculated water, controls 55 ℃ of condensator outlet temperature, analyzes the mass concentration of the zwitterion of water of condensation, reaches and moves back the salt solution index, delivers to the desalination water pot, recycles.
Embodiment 3
With mother liquor, 11Kg sodium metaaluminate or the sodium aluminate of 100kg de-salted water, 110kg, the silicon sol of 250kg mass content 26%, the hexamethylene imine of 35kg and 2kg NaMCM-49 molecular sieve add successively, and fully stir, and prepare burden, plastic and crystallization; Under 50 ℃, enter plate-and-frame filter press and isolate mother liquor.Mother liquor is squeezed into the mother liquor storage tank with the mother liquor pump; Filter cake is delivered to oxidation trough, adds the 200kg de-salted water, under 65 ℃, adds the hydrogen peroxide 30kg of mass content 30%, oxidation 5h; Oxidation is sent into plate-and-frame filter press after finishing, and 160kg filtrate is efflux wastewater; Filter cake is sent baking oven to, under 120 ℃, carries out dry 6h; Under 560 ℃, carry out roasting 15h, produce a small amount of waste gas; After cooling, put into pulping tank, add the aqueous citric acid solution of mass content 15%, deliver to the Spiralism type dynamic pressure filter, washing 20min detects Na
+ 1Ion 5ppm; Exchange 30min, solid is sent baking oven back to, under 120 ℃, dry 20h; , under 550 ℃, roasting 20h obtains HMCM-49; Liquid is with being pumped to thin-film evaporator, at 120 ℃, and flow 30m
3/ h evaporates, and steam is sent into condenser, by the flow of recirculated water, controls 65 ℃ of condensator outlet temperature, analyzes the mass concentration of the zwitterion of water of condensation, reaches and moves back the salt solution index, delivers to the desalination water pot, recycles.
Embodiment 4
With mother liquor, 11Kg sodium metaaluminate or the sodium aluminate of 80kg de-salted water, 150kg, the silicon sol of 250kg mass content 26%, the hexamethylene imine of 35kg and 2kg NaMCM-49 molecular sieve add successively, and fully stir, and prepare burden, plastic and crystallization; Under 30 ℃, enter plate-and-frame filter press and isolate mother liquor.Mother liquor is squeezed into the mother liquor storage tank with the mother liquor pump; Filter cake is delivered to oxidation trough, adds the 130kg de-salted water, under 70 ℃, adds the hydrogen peroxide 25kg of mass content 30%, oxidation 6h; Oxidation is sent into plate-and-frame filter press after finishing, and 140kg filtrate is efflux wastewater; Filter cake is sent baking oven to, under 120 ℃, and dry 16h; Under 550 ℃, roasting 25h produces a small amount of waste gas; After cooling, put into pulping tank, add the aqueous citric acid solution of mass content 5%, deliver to the Spiralism type dynamic pressure filter, washing 30min detects Na
+ 1Ion 1ppm; Exchange 20min, solid is sent baking oven back to, under 120 ℃, dry 15h; , under 550 ℃, roasting 24h obtains HMCM-49; Liquid is with being pumped to thin-film evaporator, at 120 ℃, and flow 10m
3/ h evaporates, and steam is sent into condenser, by the flow of recirculated water, controls 55 ℃ of condensator outlet temperature, analyzes the mass concentration of the zwitterion of water of condensation, reaches and moves back the salt solution index, delivers to the desalination water pot, recycles.
Embodiment 5
With mother liquor, 11Kg sodium metaaluminate or the sodium aluminate of 180kg de-salted water, 50kg, the silicon sol of 250kg mass content 26%, the hexamethylene imine of 35kg and 2kg NaMCM-49 molecular sieve add successively, and fully stir, and prepare burden, plastic and crystallization; Under 50 ℃, enter plate-and-frame filter press and isolate mother liquor.Mother liquor is squeezed into the mother liquor storage tank with the mother liquor pump; Filter cake is delivered to oxidation trough, adds the 90kg de-salted water, under 80 ℃, adds the hydrogen peroxide 30kg of mass content 26%, oxidation 4h; Oxidation is sent into plate-and-frame filter press after finishing, and 110kg filtrate is efflux wastewater; Filter cake is sent baking oven to, under 120 ℃, and dry 10h; Under 550 ℃, roasting 16h produces a small amount of waste gas; After cooling, put into pulping tank, add the aqueous citric acid solution of mass content 10%, deliver to the Spiralism type dynamic pressure filter, washing 30min detects Na
+ 1Ion 1ppm; Exchange 20min, solid is sent baking oven back to, at 120 times, dry 17h; Under 550 ℃, roasting 20h obtains HMCM-49; Liquid is with being pumped to thin-film evaporator, at 120 ℃, and flow 15m
3/ h evaporates, and steam is sent into condenser, by the flow of recirculated water, controls 55 ℃ of condensator outlet temperature, analyzes the mass concentration of the zwitterion of water of condensation, reaches and moves back the salt solution index, delivers to the desalination water pot, recycles.
Embodiment 6
With mother liquor, 11Kg sodium metaaluminate or the sodium aluminate of 120kg de-salted water, 90kg, the silicon sol of 250kg mass content 26%, the hexamethylene imine of 35kg and 2kg NaMCM-49 molecular sieve add successively, and fully stir, and prepare burden, plastic and crystallization; Under 60 ℃, enter plate-and-frame filter press and isolate mother liquor.Mother liquor is squeezed into the mother liquor storage tank with the mother liquor pump; Filter cake is delivered to oxidation trough, adds the 150kg de-salted water, under 80 ℃, adds the hydrogen peroxide 30kg of mass content 26%, oxidation 8h; Oxidation is sent into plate-and-frame filter press after finishing, and 170kg filtrate is efflux wastewater; Filter cake is sent baking oven to, under 120 ℃, and dry 10h; Under 560 ℃, roasting 10h produces a small amount of waste gas; After cooling, put into pulping tank, add the aqueous citric acid solution of mass content 10%, deliver to the Spiralism type dynamic pressure filter, washing 30min detects Na
+ 1Ion 1ppm; Exchange 20min, solid is sent baking oven back to, under 120 ℃, dry 17h; Under 540 ℃, roasting 24h obtains HMCM-49; Liquid is with being pumped to thin-film evaporator, at 120 ℃, and flow 15m
3/ h evaporates, and steam is sent into condenser, by the flow of recirculated water, controls 55 ℃ of condensator outlet temperature, analyzes the mass concentration of the zwitterion of water of condensation, reaches and moves back the salt solution index, delivers to the desalination water pot, recycles.
The comparative example
With the silicon sol of 210kg de-salted water, 11Kg sodium metaaluminate or sodium aluminate, 250kg mass content 26%, the hexamethylene imine of 35kg and 2kg NaMCM-49 molecular sieve add successively, and fully stir, and prepare burden, plastic and crystallization; Under 60 ℃, enter plate-and-frame filter press and isolate mother liquor.The 200kg mother liquor is directly drained, and filter cake is sent baking oven to, under 120 ℃, carries out dry 10h; After drying, under 560 ℃, roasting 10h produces a large amount of nitrous oxides exhaust gas; After cooling, put into pulping tank, add de-salted water to deliver to the Spiralism type dynamic pressure filter, washing 30min detects washing lotion and washs middle Na
+Ion 1ppm; With the aqueous ammonium nitrate solution of mass content 8%, exchange 20min, solid is sent baking oven back to, under 120 ℃, dry 17h; , under 540 ℃, roasting 24h obtains HMCM-49; 1500kg contains the washings of sodium and the exchanging liquid of ammonium nitrate is directly drained.
Claims (1)
1. HMCM-49 method for producing molecular sieve is characterized in that:
(1) the mother liquor 50-150kg of silicon sol 200-300kg, sodium metaaluminate or the sodium aluminate 10-20Kg of mass content 25-30%, hexamethylene imine 20-40kg, de-salted water 60-250kg, recycle and NaMCM-49 molecular sieve 1-5kg are put into a reactor mixes, plastic, crystallization;
(2) isolate mother liquor through plate-and-frame filter press, recycle; Filter cake after separation is delivered to oxidation trough, adds the 80-250kg de-salted water, under 60-85 ℃, adds mass content 30-26% hydrogen peroxide 12-50kg, oxidation 2-10h, after filtration, drying and roasting;
(3) after cooling, enter pulping tank, add the aqueous citric acid solution of mass content 5-20%, wash continuously and exchange on the Spiralism type dynamic pressure filter, washing time 20-40min, Na in molecular sieve
+ 1Ion-cleaning arrives≤10ppm; Exchange 30-50min, solid part drying, roasting obtain the HMCM-49 molecular sieve; Liquid portion is through the thin-film evaporator vaporize water, then carries out condensation with the recirculated water cooling condenser, and the de-salted water as batching use recycles.
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Citations (7)
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| US5236575A (en) * | 1991-06-19 | 1993-08-17 | Mobil Oil Corp. | Synthetic porous crystalline mcm-49, its synthesis and use |
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| CN1613768A (en) * | 2004-11-30 | 2005-05-11 | 清华大学 | Method for removing organic formwork agent in porous molecular sieve |
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| CN101279280A (en) * | 2007-04-04 | 2008-10-08 | 中国石油化工股份有限公司 | Catalyst for preparing propylene transformed from methanol |
| CN101890362A (en) * | 2009-05-19 | 2010-11-24 | 谭志平 | Fluid catalytic cracking catalyst with low coke yield and preparation method thereof |
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2011
- 2011-11-25 CN CN201110380277.8A patent/CN103130238B/en active Active
Patent Citations (7)
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| US5236575A (en) * | 1991-06-19 | 1993-08-17 | Mobil Oil Corp. | Synthetic porous crystalline mcm-49, its synthesis and use |
| CN1138007A (en) * | 1995-06-14 | 1996-12-18 | 中国石油化工总公司 | Method for removing organic template agent in ultramacroporous molecular sieve |
| CN1500726A (en) * | 2002-11-13 | 2004-06-02 | 中国石油化工股份有限公司 | Method for preparing MCM-49 molecular sieves |
| CN1613768A (en) * | 2004-11-30 | 2005-05-11 | 清华大学 | Method for removing organic formwork agent in porous molecular sieve |
| CN101279280A (en) * | 2007-04-04 | 2008-10-08 | 中国石油化工股份有限公司 | Catalyst for preparing propylene transformed from methanol |
| CN101164885A (en) * | 2007-09-26 | 2008-04-23 | 吉林大学 | Method for synthesizing kilogram-stage nano molecular screen MCM-56 and template agent removing method |
| CN101890362A (en) * | 2009-05-19 | 2010-11-24 | 谭志平 | Fluid catalytic cracking catalyst with low coke yield and preparation method thereof |
Non-Patent Citations (1)
| Title |
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| 邓广金等: "纳米MCM-49分子筛在丙烯与苯烷基化反应中的催化性能", 《石化技术》, vol. 18, no. 2, 21 June 2011 (2011-06-21), pages 5 - 8 * |
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