CN1329312C - Method for adsorbing separating methyl nitrobenzene waste water and resource recovering by zeolite - Google Patents
Method for adsorbing separating methyl nitrobenzene waste water and resource recovering by zeolite Download PDFInfo
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- CN1329312C CN1329312C CNB2004100656869A CN200410065686A CN1329312C CN 1329312 C CN1329312 C CN 1329312C CN B2004100656869 A CNB2004100656869 A CN B2004100656869A CN 200410065686 A CN200410065686 A CN 200410065686A CN 1329312 C CN1329312 C CN 1329312C
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- Prior art keywords
- nitrotoluene
- hzsm
- zeolite
- adsorption
- waste water
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- 239000010457 zeolite Substances 0.000 title claims abstract description 40
- 229910021536 Zeolite Inorganic materials 0.000 title claims abstract description 37
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 20
- 239000002351 wastewater Substances 0.000 title claims abstract description 12
- PLAZTCDQAHEYBI-UHFFFAOYSA-N 2-nitrotoluene Chemical compound CC1=CC=CC=C1[N+]([O-])=O PLAZTCDQAHEYBI-UHFFFAOYSA-N 0.000 title claims abstract description 10
- VLZLOWPYUQHHCG-UHFFFAOYSA-N nitromethylbenzene Chemical class [O-][N+](=O)CC1=CC=CC=C1 VLZLOWPYUQHHCG-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000001179 sorption measurement Methods 0.000 claims abstract description 25
- 238000000926 separation method Methods 0.000 claims abstract description 15
- 230000003068 static effect Effects 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000010815 organic waste Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 4
- 238000002203 pretreatment Methods 0.000 claims description 3
- 238000004064 recycling Methods 0.000 claims description 3
- 238000007789 sealing Methods 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 2
- ZPTVNYMJQHSSEA-UHFFFAOYSA-N 4-nitrotoluene Chemical compound CC1=CC=C([N+]([O-])=O)C=C1 ZPTVNYMJQHSSEA-UHFFFAOYSA-N 0.000 abstract description 18
- 239000002245 particle Substances 0.000 abstract description 2
- 239000008187 granular material Substances 0.000 abstract 1
- 238000011084 recovery Methods 0.000 description 9
- 230000000694 effects Effects 0.000 description 6
- 239000011148 porous material Substances 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 239000002594 sorbent Substances 0.000 description 2
- CZGCEKJOLUNIFY-UHFFFAOYSA-N 4-Chloronitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(Cl)C=C1 CZGCEKJOLUNIFY-UHFFFAOYSA-N 0.000 description 1
- CZEVYBDBEQCIDJ-UHFFFAOYSA-N 5-methyl-5-nitrocyclohexa-1,3-diene Chemical compound [O-][N+](=O)C1(C)CC=CC=C1 CZEVYBDBEQCIDJ-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910004283 SiO 4 Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000002894 chemical waste Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000002414 normal-phase solid-phase extraction Methods 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 229910021426 porous silicon Inorganic materials 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000009967 tasteless effect Effects 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The present invention discloses an adsorption and separation technique which uses the selective adsorption action of HZSM-5 zeolites to separate organic wastewater with similar properties and nitrotoluene isomers. The method uses HZSM-5 zeolites to adsorb and separate waste water containing nitrotoluene so as to recover resources and uses the way of static treatment; and organic wastewater to be treated and containing nitrotoluene isomers is conveyed to an adsorption container for adsorption. The adsorption has the conditions that the particle diameter of the HZSM-5 zeolites is from 0.5 to 20 mu m, the initial concentration ratio of o-nitrotoluene to p-nitrotoluene is from 1-5 to 1; the mass ratio of the p-nitrotoluene to HZSM-5 zeolite granules before processing is from 0.02 to 0.1; the vibratory rotation speed is from 50 to 200 revolutions per minute; the temperature interval is from 275 to 340K; and the adsorption time is from 10 seconds to 12 hours. The method has the advantages of high efficiency, low consumption, and wide application perspective.
Description
Technical field
The present invention relates to a kind of adsorption separation technology, utilize the selective adsorption effect of HZSM-5 zeolite, separating purifies contains the organic waste water of nitrotoluene isomer.
Background technology
Absorption is a kind of Solid-Phase Extraction isolation technique of less energy-consumption.Adsorption be since the molecule of solid surface or atom because of discontinuity equalization has remaining surface energy.When some materials collision solid surface, be subjected to the attraction of these unbalanced forces and be trapped on the solid surface, make be adsorbed molecule adsorbent surface concentration be higher than the solution body mutually in concentration.Handle the sorbent material that meticulous organic chemical waste water mainly adopts with absorption method gac, modified-cellulose and resin etc. are arranged.The charcoal absorption performance is preferable, but its regeneration difficulty (needing superheated vapour and comparatively high temps), the material of absorption is difficult to realize resource utilization.Polymeric adsorbent is applied and forms a kind of adsorption separation technology of uniqueness in every field.But existing resin choice is not high, and is also very difficult for effective separation of close organism isomer of character or homologue.
Zeolite is a kind of porous silicon aluminate crystal, is by silica (SiO
4) tetrahedron and alumina (AlO
4) tetrahedron element is staggered to spacial framework by the Sauerstoffatom that is in tetrahedron top.Exist a large amount of holes in crystalline structure, movably water molecules and positively charged ion are distributing in the hole.This constructional feature makes zeolite have absorption, catalysis and the ion-exchange three big characteristics of selection.HZSM-5 belongs to mesopore zeolite, has the pore canal system that 3 D stereo intersects, and channel diameter is 0.51 * 0.55nm, 0.54 * 0.56nm, and these two kinds of dissimilar ducts diameter in the vertical point of crossing that forms mutually are 0.89nm.Because its uniform micropore is suitable with the molecular size of general material, formed the selection characterization of adsorption of molecular sieve thus, be the molecular size that the size decision of HZSM-5 zeolite pore can enter its bug hole inside, have only molecule or the ion littler just can enter than zeolite pore.In the isomers of nitrotoluene, the critical kinetic diameter of para-isomeride is slightly smaller than the channel diameter of HZSM-5 zeolite, and ortho position and meta-isomer are big than the channel diameter of HZSM-5 zeolite.Like this because the inhibition in duct, make neighbour position of the less para-isomeride of molecule critical diameter and meta-isomer be easier to be diffused in the hole in and be adsorbed on the active centre of internal surface, show para-isomeride is had the performance that selection is adsorbed.
Summary of the invention
The purpose of this invention is to provide a kind of adsorption separation technology, utilize the selection adsorption of HZSM-5 zeolite, the organic waste water that contains the nitrotoluene isomer that separating property is close.
Technical scheme of the present invention is as follows:
A kind of with zeolite adsorption separation methyl nitrobenzene waste water and resource recycling method, it is characterized in that adopting the static treatment method, the organic waste water that contains the nitrotoluene isomer that will handle is delivered to contactor and adsorbs, and adsorption conditions is: HZSM-5 zeolite granular diameter is 0.5～20 μ m; The starting point concentration ratio of ortho position nitrotoluene and contraposition nitrotoluene is 1～5: 1; The mass ratio of contraposition nitrotoluene and HZSM-5 zeolite granular is 0.02～0.1 before handling; The vibration rotating speed is 50～200 rev/mins; Temperature range is 275～340K; Adsorption time is 10s～12h.
Mass ratio the best of contraposition nitrotoluene and HZSM-5 zeolite granular is 0.05 before handling.
The HZSM-5 zeolite is used rare HNO before use
3Handle, and oven dry, rare HNO
3Be 1%HNO3.
HZSM-5 zeolite granular diameter is 0.5～20 μ m; The starting point concentration ratio of ortho position nitrotoluene and contraposition nitrotoluene is 1～2: 1; The vibration rotating speed is 100～150 rev/mins; Temperature range is 278～323K; Adsorption time is 10s～2h.
Before methyl nitrobenzene waste water enters contactor, need carry out some conventional pre-treatment, as filtering etc.
Stirring can be adopted the constant temperature cradle vibrate, also can adopt constant temperature blender with magnetic force to stir.
Contactor sealing or opening.
The separating effect of nitrotoluene isomer is relevant with its character and molecular diameter.The molecular size that the size decision of HZSM-5 zeolite pore can enter its bug hole inside has only molecule or the ion littler than zeolite pore just can enter.
The separating effect of organism isomer is relevant with HZSM-5 zeolite surface structure.The non-selective acidic site of passivation HZSM-5 zeolite surface and compression HZSM-5 zeolite pore can improve the separating effect of organism isomer.The separating effect of contraposition nitrotoluene is better than the separating effect of contraposition nitrotoluene.
When the present invention is used to handle the organic waste water that contains the nitrotoluene isomer, can be so that the separation efficiency of para-isomeride from mixed solution be higher than more than 99.5%, and have the higher rate of recovery, efficient low-consume has been realized the resource utilization of waste water.Simultaneously, the HZSM-5 zeolite be a kind of nontoxic, tasteless, environment is not had the sorbent material of influence, and fabulous acid resistance, thermostability and water vapour stability are arranged.Therefore, the present invention is used to handle organic waste water and has good economic benefit and environmental benefit.Efficient low-consume of the present invention has broad application prospects.
Embodiment
Below by example the present invention is done to describe further.
Embodiment 1: in the process for producing nitrotoluene process alkali cleaning waste water, get this waste water 400ml, wherein the para-nitrotoluene starting point concentration is 50.0mg/L, getting HZSM-5 zeolite quality is 0.45g.HZSM-5 zeolite Si/Al is 48; Average diameter of particles is 5 μ m; The contactor sealing; Adopt magnetic agitation, the vibration rotating speed is 150 rev/mins; The Ortho Nitro Toluene starting point concentration is 1: 1 with the ratio of para-nitrotoluene starting point concentration; Temperature is got 300K; Adsorption time is 20min.The separation rate of para-nitrotoluene is up to more than 98.8%.Adopt ethanol as reclaiming liquid, the rate of recovery of para-nitrotoluene is 98.5% when 303K.
Embodiment 2: with HZSM-5 zeolite Si/Al among the embodiment 1 is 10, and other operational condition remains unchanged, and the rate of recovery of para-nitrotoluene is suitable with embodiment 1.
Embodiment 3: with HZSM-5 zeolite Si/Al among the embodiment 1 is infinitely great, does not promptly contain Al in the zeolite, and other operational condition remains unchanged, and the rate of recovery of para-nitrotoluene is poor slightly than embodiment 1.
Embodiment 4: among the embodiment 1, other condition is constant, and when adsorption time was 5min, the separation rate of para-nitrotoluene reached more than 97.1%; When adsorption time was 60min, the separation rate of para-nitrotoluene was 97.3%.
Embodiment 5: change the ratio of the Ortho Nitro Toluene starting point concentration among the embodiment 1 and para-nitrotoluene starting point concentration into 2: 1, other operational condition remains unchanged, and the separation rate of para-nitrotoluene and Ortho Nitro Toluene is 98.2%.
Embodiment 6: among the embodiment 1, other condition is constant, and when temperature was got 278K, the separation rate of para-nitrotoluene was 99.0%; When temperature was got 323K, the separation rate of p-Nitrophenyl chloride was 97.0%.
Embodiment 7: the closed container among the embodiment 1 is changed into uncovered, other operational condition remains unchanged, and the separation rate of para-nitrotoluene is constant substantially.
Embodiment 8: change the eluting temperature among the embodiment 1 into 320K, other operational condition remains unchanged, and the rate of recovery of para-nitrotoluene reaches 99.5%.
Embodiment 9: change the recovery liquid among the embodiment 1 into methyl alcohol, other operational condition remains unchanged, and the rate of recovery of para-nitrotoluene is 86.9%.
Embodiment 10: the mass ratio of contraposition nitrotoluene and HZSM-5 zeolite granular is about 0.04 before handling among the embodiment 1, now changes the two mass ratio into 0.02, and other operational condition remains unchanged, and the rate of recovery of para-nitrotoluene is poor slightly than embodiment 1.
Embodiment 11: the mass ratio of contraposition nitrotoluene and HZSM-5 zeolite granular is about 0.04 before handling among the embodiment 1, now changes the two mass ratio into 0.09, and other operational condition remains unchanged, and the rate of recovery of para-nitrotoluene is suitable with embodiment 1.
Claims (9)
1, a kind of with zeolite adsorption separation methyl nitrobenzene waste water and resource recycling method, it is characterized in that adopting the static treatment method, the organic waste water that contains the nitrotoluene isomer that will handle is delivered to contactor and adsorbs, and adsorption conditions is: HZSM-5 zeolite granular diameter is 0.5～20 μ m; The starting point concentration ratio of ortho position nitrotoluene and contraposition nitrotoluene is 1～5: 1; The mass ratio of contraposition nitrotoluene and HZSM-5 zeolite granular is 0.02～0.05 before handling; The vibration rotating speed is 50～200 rev/mins; Temperature range is 275～340K; Adsorption time is 10s～12h.
2, method according to claim 1, the mass ratio of contraposition nitrotoluene and HZSM-5 zeolite granular is 0.05 before it is characterized in that handling.
3, method according to claim 1 is characterized in that the HZSM-5 zeolite uses rare HNO before use
3Handle, and oven dry.
4, method according to claim 3 is characterized in that described rare HNO
3Be 1%HNO
3
5, method according to claim 1 is characterized in that: HZSM-5 zeolite granular diameter is 0.5～20 μ m; The starting point concentration ratio of ortho position nitrotoluene and contraposition nitrotoluene is 1～2: 1; The vibration rotating speed is 100～150 rev/mins; Temperature range is 278～323K; Adsorption time is 10s～2h.
6, method according to claim 1 is characterized in that before methyl nitrobenzene waste water enters contactor, need carry out some conventional pre-treatment.
7, method according to claim 6 is characterized in that described conventional pre-treatment is for filtering.
8, method according to claim 1 is characterized in that stirring and adopts the constant temperature cradle vibrate or adopt constant temperature blender with magnetic force to stir.
9, method according to claim 1 is characterized in that contactor sealing or opening.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100656869A CN1329312C (en) | 2004-11-12 | 2004-11-12 | Method for adsorbing separating methyl nitrobenzene waste water and resource recovering by zeolite |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100656869A CN1329312C (en) | 2004-11-12 | 2004-11-12 | Method for adsorbing separating methyl nitrobenzene waste water and resource recovering by zeolite |
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| Publication Number | Publication Date |
|---|---|
| CN1613783A CN1613783A (en) | 2005-05-11 |
| CN1329312C true CN1329312C (en) | 2007-08-01 |
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|---|---|---|---|
| CNB2004100656869A Expired - Fee Related CN1329312C (en) | 2004-11-12 | 2004-11-12 | Method for adsorbing separating methyl nitrobenzene waste water and resource recovering by zeolite |
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1490255A (en) * | 2003-09-12 | 2004-04-21 | �Ϻ���ͨ��ѧ | Method for separating nitrochlorobenzene and nitrophenol waste water by HZSM-5 zeolites and resource recovery |
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2004
- 2004-11-12 CN CNB2004100656869A patent/CN1329312C/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1490255A (en) * | 2003-09-12 | 2004-04-21 | �Ϻ���ͨ��ѧ | Method for separating nitrochlorobenzene and nitrophenol waste water by HZSM-5 zeolites and resource recovery |
Non-Patent Citations (4)
| Title |
|---|
| 填充柱（ECD）一顶空气相色谱法测定水和废水中硝基苯、硝基甲苯和硝基氯苯 韩长绵，环境科学与技术，第2期 1996 * |
| 沸石在水和废水处理中的应用 何少华，黄仕元，金必慧，矿业工程，第2卷第1期 2004 * |
| 沸石在水和废水处理中的应用 何少华，黄仕元，金必慧，矿业工程，第2卷第1期 2004;填充柱（ECD）一顶空气相色谱法测定水和废水中硝基苯、硝基甲苯和硝基氯苯 韩长绵，环境科学与技术，第2期 1996;蓄香族硝基化合物废水处理研究 刘晓超，马丽丽，交通环保，第25卷第1期 2004 * |
| 蓄香族硝基化合物废水处理研究 刘晓超，马丽丽，交通环保，第25卷第1期 2004 * |
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