CN103130238B - HMCM-49 molecular sieve production method - Google Patents
HMCM-49 molecular sieve production method Download PDFInfo
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- CN103130238B CN103130238B CN201110380277.8A CN201110380277A CN103130238B CN 103130238 B CN103130238 B CN 103130238B CN 201110380277 A CN201110380277 A CN 201110380277A CN 103130238 B CN103130238 B CN 103130238B
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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:
HMCM-49 molecular sieve is preparation HMCM-49 catalyzer direct material, carry out plastic and crystallization by silicon sol, sodium aluminate (or sodium metaaluminate) aqueous solution and hexamethylene imine, isolate mother liquor, produce NaMCM-49 molecular sieve, exchange through aqueous ammonium nitrate solution, carry out drying and roasting, produce HMCM-49 molecular sieve.
At present, produce HMCM-49 molecular sieve, in the process of plastic and crystallization, its reaction is carried out in aqueous, directly enter mother liquor containing a certain amount of unreacted hexamethylene imine, usual mother liquor directly discharges as waste water, owing to containing 8-12% hexamethylene imine in mother liquor, hexamethylene imine is expensive on the one hand, and directly discharge increases 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 by the template of molecular sieve endoporus, thermal degradation, hexamethylene imine thermal degradation becomes oxynitrides and carbonic acid gas, and this step produces waste gas generating step in HMCM-49 molecular sieve process, is produce urgent problem.NaMCM-49 molecular sieve is gone out through baked for producing, wash through de-salted water, deviate from free alkali (sodium hydroxide), consume a large amount of de-salted waters, exchange 3-4 time with 8-10% aqueous ammonium nitrate solution afterwards, produce a large amount of nitrogenous effluent, these two processes produce a large amount of waste water, are also to produce urgent problem.
Chinese patent 02145237.7 proposes a kind of preparation method of MCM-49 molecular sieve, partial mother liquid is circulated, the remaining hexamethylene imine of recovery part, but also reclaims hexamethylene imine and the thorough problem solving hexamethylene imine waste water straightly discharging completely.
Summary of the invention
The object of the invention is the HMCM-49 method for producing molecular sieve providing a kind of waste water, waste gas and waste sludge discharge few, and the method is the mother liquor will separated after crystallization, circulates completely; With hydrogen peroxide oxidation part hexamethylene imine, reduce the discharge of the waste gas of oxynitride; Washing and exchange, adopt sodium citrate aqueous solution, thoroughly effected a radical cure ammonium nitrogen wastewater generation.The present invention will prepare burden, plastic, crystallization proceed step by step in same reactor, simplify production unit, by adopting Spiralism type dynamic pressure filter, simplify production process, decreasing the labour intensity of operation.
The technical solution used in the present invention is as follows:
(1) ratio of mother liquor 50-150kg, NaMCM-49 molecular sieve 1-5kg of the silicon sol 200-300kg of mass content 25-30%, sodium metaaluminate or sodium aluminate 10-20Kg, hexamethylene imine 20-40kg, de-salted water 60-250kg, recycle is carried out in a reactor mix, plastic, crystallization;
(2) isolate mother liquor through plate-and-frame filter press, recycle; Oxidation trough delivered to by filter cake after separation, adds 80-250kg de-salted water, at 60-85 DEG C, adds 30-26% hydrogen peroxide 12-50kg, oxidation 2-10h, after filtration, dry and roasting, and removing hexamethylene imine;
(3), after cooling, enter pulping tank, add the aqueous citric acid solution of 5-20% mass content, Spiralism type dynamic pressure filter carries out continuously wash and exchange, washing time 20-40min, Na in molecular sieve
+ 1ion-cleaning is to below 10ppm; Exchange 30-50min, solid part drying, roasting, obtain HMCM-49 molecular sieve; Liquid portion through thin-film evaporator vaporize water, then carries out condensation with recirculated water cooling condenser, as the de-salted water of batching, 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 the solid obtained from vaporizer is Trisodium Citrate.From wastewater discharge, be 1/20th of traditional technology, waste gas is 1/1/2nd ~ tri-of traditional technology, and solid citric acid sodium waste residue can be demoted use.
Batching of the present invention, plastic, crystallization are all carried out in plastic crystallizing kettle, save material-compound tank and colloid generating kettle, save facility investment; The mother liquor that plate-and-frame filter press is separated, can be recycled, and decreases the discharge of waste water.
Embodiment
Embodiment 1
By the silicon sol of the mother liquor of 100kg de-salted water, 110kg, 11kg sodium metaaluminate or sodium aluminate, 250kg mass content 26%, hexamethylene imine and the 2kg NaMCM-49 molecular sieve of 35kg add successively, and fully stir, and carry out preparing burden, plastic and crystallization; At 40 DEG C, enter plate-and-frame filter press and isolate mother liquor.Mother liquor storage tank squeezed into by mother liquor mother liquor pump; Oxidation trough delivered to by filter cake, adds 90kg de-salted water, at 65 DEG C, adds the hydrogen peroxide 15kg of mass content 30%, oxidation 5h; After oxidation terminates, send into plate-and-frame filter press, 80kg filtrate is efflux wastewater; Baking oven sent to by filter cake, at 120 DEG C, carries out dry 6h; After drying, at 550 DEG C, 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 Spiralism type dynamic pressure filter, washing 20min, detects Na
+ 1ion 5ppm; Exchange 30min, baking oven sent back to by solid, at 120 DEG C, and dry 8h; , at 550 DEG C, roasting 18h, obtains HMCM-49; Liquid with being pumped to thin-film evaporator, at 120 DEG C, flow 20m
3/ h, evaporates, and steam sends into condenser, by the flow of recirculated water, controls condensator outlet temperature 65 DEG C, analyzes the mass concentration of the zwitterion of water of condensation, reach and move back salt solution index, deliver to desalination water pot, recycle.
Embodiment 2
By the silicon sol of the mother liquor of 70kg de-salted water, 150kg, 11Kg sodium metaaluminate or sodium aluminate, 250kg mass content 26%.Hexamethylene imine and the 2kg NaMCM-49 molecular sieve of 35kg add successively, and fully stir, and carry out preparing burden, plastic and crystallization; At 60 DEG C, enter plate-and-frame filter press and isolate mother liquor, mother liquor storage tank squeezed into by mother liquor mother liquor pump; Oxidation trough delivered to by filter cake, adds 120kg de-salted water, at 65 DEG C, adds the hydrogen peroxide 20kg of mass content 30%, oxidation 4h; After oxidation terminates, send into plate-and-frame filter press, filtrate 100kg is efflux wastewater; Baking oven sent to by filter cake, at 120 DEG C, carries out dry 10h; At 540 DEG C, 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 Spiralism type dynamic pressure filter, washing 30min, detects Na
+ 1ion 1ppm; Exchange 20min, baking oven sent back to by solid, at 120 DEG C, and dry 8h; , at 550 DEG C, roasting 16h, obtains HMCM-49; Liquid with being pumped to thin-film evaporator, at 110 DEG C, flow 10m
3/ h, evaporates, and steam sends into condenser, by the flow of recirculated water, controls condensator outlet temperature 55 DEG C, analyzes the mass concentration of the zwitterion of water of condensation, reach and move back salt solution index, deliver to desalination water pot, recycle.
Embodiment 3
By the silicon sol of the mother liquor of 100kg de-salted water, 110kg, 11Kg sodium metaaluminate or sodium aluminate, 250kg mass content 26%, hexamethylene imine and the 2kg NaMCM-49 molecular sieve of 35kg add successively, and fully stir, and carry out preparing burden, plastic and crystallization; At 50 DEG C, enter plate-and-frame filter press and isolate mother liquor.Mother liquor storage tank squeezed into by mother liquor mother liquor pump; Oxidation trough delivered to by filter cake, adds 200kg de-salted water, at 65 DEG C, adds the hydrogen peroxide 30kg of mass content 30%, oxidation 5h; After oxidation terminates, send into plate-and-frame filter press, 160kg filtrate is efflux wastewater; Baking oven sent to by filter cake, at 120 DEG C, carries out dry 6h; At 560 DEG C, 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 Spiralism type dynamic pressure filter, washing 20min, detects Na
+ 1ion 5ppm; Exchange 30min, baking oven sent back to by solid, at 120 DEG C, and dry 20h; , at 550 DEG C, roasting 20h, obtains HMCM-49; Liquid with being pumped to thin-film evaporator, at 120 DEG C, flow 30m
3/ h, evaporates, and steam sends into condenser, by the flow of recirculated water, controls condensator outlet temperature 65 DEG C, analyzes the mass concentration of the zwitterion of water of condensation, reach and move back salt solution index, deliver to desalination water pot, recycle.
Embodiment 4
By the silicon sol of the mother liquor of 80kg de-salted water, 150kg, 11Kg sodium metaaluminate or sodium aluminate, 250kg mass content 26%, hexamethylene imine and the 2kg NaMCM-49 molecular sieve of 35kg add successively, and fully stir, and carry out preparing burden, plastic and crystallization; At 30 DEG C, enter plate-and-frame filter press and isolate mother liquor.Mother liquor storage tank squeezed into by mother liquor mother liquor pump; Oxidation trough delivered to by filter cake, adds 130kg de-salted water, at 70 DEG C, adds the hydrogen peroxide 25kg of mass content 30%, oxidation 6h; After oxidation terminates, send into plate-and-frame filter press, 140kg filtrate is efflux wastewater; Baking oven sent to by filter cake, at 120 DEG C, and dry 16h; At 550 DEG C, 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 Spiralism type dynamic pressure filter, washing 30min, detects Na
+ 1ion 1ppm; Exchange 20min, baking oven sent back to by solid, at 120 DEG C, and dry 15h; , at 550 DEG C, roasting 24h, obtains HMCM-49; Liquid with being pumped to thin-film evaporator, at 120 DEG C, flow 10m
3/ h, evaporates, and steam sends into condenser, by the flow of recirculated water, controls condensator outlet temperature 55 DEG C, analyzes the mass concentration of the zwitterion of water of condensation, reach and move back salt solution index, deliver to desalination water pot, recycle.
Embodiment 5
By the silicon sol of the mother liquor of 180kg de-salted water, 50kg, 11Kg sodium metaaluminate or sodium aluminate, 250kg mass content 26%, hexamethylene imine and the 2kg NaMCM-49 molecular sieve of 35kg add successively, and fully stir, and carry out preparing burden, plastic and crystallization; At 50 DEG C, enter plate-and-frame filter press and isolate mother liquor.Mother liquor storage tank squeezed into by mother liquor mother liquor pump; Oxidation trough delivered to by filter cake, adds 90kg de-salted water, at 80 DEG C, adds the hydrogen peroxide 30kg of mass content 26%, oxidation 4h; After oxidation terminates, send into plate-and-frame filter press, 110kg filtrate is efflux wastewater; Baking oven sent to by filter cake, at 120 DEG C, and dry 10h; At 550 DEG C, 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 Spiralism type dynamic pressure filter, washing 30min, detects Na
+ 1ion 1ppm; Exchange 20min, baking oven sent back to by solid, at 120 times, and dry 17h; At 550 DEG C, roasting 20h, obtains HMCM-49; Liquid with being pumped to thin-film evaporator, at 120 DEG C, flow 15m
3/ h, evaporates, and steam sends into condenser, by the flow of recirculated water, controls condensator outlet temperature 55 DEG C, analyzes the mass concentration of the zwitterion of water of condensation, reach and move back salt solution index, deliver to desalination water pot, recycle.
Embodiment 6
By the silicon sol of the mother liquor of 120kg de-salted water, 90kg, 11Kg sodium metaaluminate or sodium aluminate, 250kg mass content 26%, hexamethylene imine and the 2kg NaMCM-49 molecular sieve of 35kg add successively, and fully stir, and carry out preparing burden, plastic and crystallization; At 60 DEG C, enter plate-and-frame filter press and isolate mother liquor.Mother liquor storage tank squeezed into by mother liquor mother liquor pump; Oxidation trough delivered to by filter cake, adds 150kg de-salted water, at 80 DEG C, adds the hydrogen peroxide 30kg of mass content 26%, oxidation 8h; After oxidation terminates, send into plate-and-frame filter press, 170kg filtrate is efflux wastewater; Baking oven sent to by filter cake, at 120 DEG C, and dry 10h; At 560 DEG C, 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 Spiralism type dynamic pressure filter, washing 30min, detects Na
+ 1ion 1ppm; Exchange 20min, baking oven sent back to by solid, at 120 DEG C, and dry 17h; At 540 DEG C, roasting 24h, obtains HMCM-49; Liquid with being pumped to thin-film evaporator, at 120 DEG C, flow 15m
3/ h, evaporates, and steam sends into condenser, by the flow of recirculated water, controls condensator outlet temperature 55 DEG C, analyzes the mass concentration of the zwitterion of water of condensation, reach and move back salt solution index, deliver to desalination water pot, recycle.
Comparative example
By the silicon sol of 210kg de-salted water, 11Kg sodium metaaluminate or sodium aluminate, 250kg mass content 26%, hexamethylene imine and the 2kg NaMCM-49 molecular sieve of 35kg add successively, and fully stir, and carry out preparing burden, plastic and crystallization; At 60 DEG C, enter plate-and-frame filter press and isolate mother liquor.200kg mother liquor is directly drained, and baking oven sent to by filter cake, at 120 DEG C, carries out dry 10h; After drying, at 560 DEG C, roasting 10h, produces a large amount of nitrous oxides exhaust gas; After cooling, put into pulping tank, add de-salted water and deliver to Spiralism type dynamic pressure filter, washing 30min, detect washing lotion and wash middle Na
+ion 1ppm; With the aqueous ammonium nitrate solution of mass content 8%, exchange 20min, baking oven sent back to by solid, at 120 DEG C, and dry 17h; , at 540 DEG C, roasting 24h, obtains HMCM-49; 1500kg directly drains containing the washings of sodium and the exchanging liquid of ammonium nitrate.
Claims (1)
1. a HMCM-49 method for producing molecular sieve, is characterized in that:
(1) the mother liquor 50-150kg of the silicon sol 200-300kg of mass content 25-30%, sodium metaaluminate or sodium aluminate 10-20Kg, hexamethylene imine 20-40kg, de-salted water 60-250kg, recycle and NaMCM-49 molecular sieve 1-5kg is put into that a reactor carries out mixing, plastic, crystallization;
(2) isolate mother liquor through plate-and-frame filter press, recycle; Oxidation trough delivered to by filter cake after separation, adds 80-250kg de-salted water, at 60-85 DEG C, adds mass content 30-26% hydrogen peroxide 12-50kg, oxidation 2-10h, after filtration, dry and roasting;
(3), after cooling, enter pulping tank, add the aqueous citric acid solution of mass content 5-20%, Spiralism type dynamic pressure filter carries out continuously wash and exchange, washing time 20-40min, Na in molecular sieve
+ 1ion-cleaning is to≤10ppm; Exchange 30-50min, solid part drying, roasting, obtain HMCM-49 molecular sieve; Liquid portion through thin-film evaporator vaporize water, then carries out condensation with recirculated water cooling condenser, as the de-salted water of batching, recycles.
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2011
- 2011-11-25 CN CN201110380277.8A patent/CN103130238B/en active Active
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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 |
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