CN1169731C - Circular utilization of Y-type molecular sieve exchange washing water - Google Patents
Circular utilization of Y-type molecular sieve exchange washing water Download PDFInfo
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- CN1169731C CN1169731C CNB021169241A CN02116924A CN1169731C CN 1169731 C CN1169731 C CN 1169731C CN B021169241 A CNB021169241 A CN B021169241A CN 02116924 A CN02116924 A CN 02116924A CN 1169731 C CN1169731 C CN 1169731C
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- Prior art keywords
- molecular sieve
- clear liquid
- add
- exchange
- washing water
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Abstract
The present invention relates to a circulatory utilization method for exchange wash water of a Y type molecular sieve, which mainly comprises the following procedures: (1) flocculating agents are added to exchange wash water of a Y type molecular sieve to be stirred to form clear solutions and solid precipitates; (2) the clear solutions and the solid precipitates are separated; (3)the clear solutions obtained in the procedure (2) pass through cation exchange resin; (4) the clear solutions obtained in the procedure (3) are prepared into exchange solutions of a molecular sieve for circulatory utilization. The method can effectively reduce the cost for preparing molecular sieves and reduce sewage discharge.
Description
Technical field
The present invention relates to the method for wastewater treatment in the catalyst preparation process, more particularly, is the recycle method of Y zeolite exchange washing water.
Background technology
Cracking catalyst is the important integral part of catalytic cracking process, and the quality of its performance will directly have influence on the productive rate and the quality of purpose product, plays a part very important to the economic benefit of oil refining enterprise.Y zeolite has become the main active component of cracking catalyst soon since coming out.Up to the present, REY, REHY and super-stable Y molecular sieves remain irreplaceable active ingredient in the catalytic cracking catalyst.In the preparation process of Y zeolite, ion-exchange and the washing step that is absolutely necessary.In exchange and washing process, need to exchange, to filter with the salts solution and the molecular sieve of certain proportioning, and then with chemical water (remove positively charged ion after tap water) washing leaching cake, thereby reach Na in the reduction molecular sieve
2The purpose of O content.
According to present technology, exchange process mainly contains the exchange of still formula and the band filter continuous countercurrent exchanges two kinds, and total water consumption is 10-15 a times of molecular sieve, and exchange solution is mainly by fresh decationizing water, NH
3H
2O, H
2SO
4, HCl etc. are formulated according to a certain ratio, and after exchange solution mixed, contacts, filters with molecular sieve after heating up, its filtrate and washing water directly were discharged into wastewater disposal basin.Contain Na in the waste water of Y zeolite washing exchange
+, SO
4 2-, NH
4 +With the solid substance about 1 heavy %.These solid substances mainly are the molecular sieve fine powders with polarity and strong adsorptivity.
CN1192998A has disclosed a kind of technological process for the treatment of papermaking method.This method is that sewage is introduced the sewage storage pool earlier, puts into treatment tank again, drops into the chemicals of working good, and stirs then, precipitates, and post precipitation drains into clean water basin with clear water respectively, and throw out is sent into throw out and deposited the pond, redeposition and filter dehydration.This method cost is low, takes up an area of to lack, and the treatment time is short, and civil engineering and facility investment are little, and little power consumption and treatment capacity are big, and the water after the processing can reach national specified discharge standard.
CN1197768A discloses a kind of general method of wastewater treatment.This method is with lime or contains CaO or Ca (OH)
2Material and acid effect, form throw out; In forming the throw out process and after throw out forms, adsorb and carry charged impurity particle and electric neutrality impurity particle in the waste water secretly, realize processing various wastewater.
Summary of the invention
The objective of the invention is to provide on the basis of existing technology a kind of molecular sieve exchange washing water recycle method, thus the production cost of water saving, reduction molecular sieve.
Method provided by the invention may further comprise the steps: (1) adds flocculation agent in molecular sieve exchange washing water, is stirred to form clear liquid and solid shape throw out; (2) separate above-mentioned clear liquid and solid shape throw out; (3) step (2) gained clear liquid passes through Zeo-karb; (4) step (3) gained clear liquid being mixed with molecular sieve exchange solution circulated uses.
Compared with prior art, beneficial effect of the present invention is mainly reflected in the following aspects:
1. method provided by the invention is easy and simple to handle, easy to implement.Molecular sieve exchange washing water promptly can be recycled after the present invention handles.
2. adopt method provided by the invention, can make the water loss of molecular sieve preparation process reduce by 20～50%.
3. the present invention utilizes the cationic exchange technology to remove part Na in the molecular sieve exchange washing water
+Ion, the clear liquid after the processing recycles after allotment.Therefore, the present invention can reduce sewage discharge, water saving, protection environment, and economic benefit and social benefit all are tangible.
Embodiment
To be further specified method provided by the invention below, but therefore not make the present invention be subjected to any restriction.
Method provided by the invention mainly may further comprise the steps:
Step (1): add cationic polyacrylamide or anionic polyacrylamide in molecular sieve exchange washing water, its add-on is 5～20ppm, and preferred 8～15ppm stirred 2 minutes at least; Add polymerization AlCl then
3, its add-on is 1～10ppm, preferred 2～8ppm continues to be stirred to formation clear liquid and solid shape throw out.
Step (2): separate above-mentioned clear liquid and solid shape throw out with deep bed filter or other this area strainer commonly used.As weighting material, and their particle diameter is 0.7～2.0mm to selected deep bed filter with quartz sand and/or slag, and preferred 0.8～1.5mm, bed height are 300～1000mm, preferred 400～900mm.Flow through behind the deep bed filter from the clear liquid of step (1) and solid shape throw out, can obtain turbidity and be 10～20 clear liquid.
Step (3): step (2) gained clear liquid is by being filled with the cationic exchange coloum of Zeo-karb, the Na in the clear liquid
+With the H on the ion exchange resin
+Exchange, thus make Na in the clear liquid
+Content reduce to 0.1～0.6 heavy %.The present invention does not have particular requirement to the described Zeo-karb of step (3), and Zeo-karbs such as macroporous type, gel-type, strong acid type, weak-type all can be used for the present invention.
Step (4): step (3) gained clear liquid is mixed with molecular sieve exchange solution circulated uses.
Clear liquid after the present invention handles promptly can be used for preparing molecular sieve exchange solution, and its compound method and ordinary method are basic identical, for example, adds the NH of specified amount in step (3) gained clear liquid
4 +, SO
4 2-, Cl
-Plasma is mixed with exchange solution, utilizes this exchange solution to carry out the molecular sieve exchange, filter, wash, and the sodium content of handling the back molecular sieve meets the demands substantially.
Y zeolite exchange washing water of the present invention is the mixture that exchanges mother liquor and washing water in the molecular sieve preparation process, and the blending ratio of the two is 2～3: 1.
The following examples will give further instruction to method provided by the invention, but not thereby limiting the invention.
Embodiment 1
The present embodiment explanation: after adopting method provided by the invention that molecular sieve exchange washing water is handled, the gained clear liquid can be mixed with molecular sieve exchange solution circulated and use.
Testing sequence is as follows: (1) is (its Na in the mixed solution of NaY molecular sieve exchange mother liquor and washing water
+Content is 1.06 heavy %) add the 5ppm cationic polyacrylamide, stirred 3 minutes, add 10ppm polymerization AlCl then
3, continue to stir after 2 minutes and leave standstill.Flocculent precipitate sinks rapidly.(2) supernatant liquid (turbidity is 12) is delivered to deep bed filter.Quartz sand is housed in the strainer, and bed height 500mm, quartz sand particle size are 0.7～1.1mm.Flow through behind the deep bed filter, the turbidity of clear liquid is 11.(3) clear liquid that step (2) is obtained carries out ion-exchange with being pumped into cationic exchange coloum, the Na of exchange back clear liquid
+Content is 0.2 heavy %.(4) in step (3) gained clear liquid, add NH
4Cl and HCl, the pH value to 3.3 of regulator solution, and to make the concentration of ammonium chloride be 10 heavy %, exchanges Na in the NaY molecular sieve filter cake of exchange back again with the NaY molecular sieve
+Content is 5.3 heavy %.And after the exchange solution exchange with fresh decationizing water configuration, Na in the molecular sieve filter cake
+Content is 5.0 heavy %.Repeating step (4), just the ammonium chloride concentration that adds is increased to 13 heavy %, Na in the resulting NaY molecular sieve filter cake
+Content 5.0 heavy %.
Embodiment 2
The present embodiment explanation: after adopting method provided by the invention that molecular sieve exchange washing water is handled, the gained clear liquid can be mixed with molecular sieve exchange solution circulated and use.
Testing sequence is as follows: (1) is (its Na in the mixed solution of NaY molecular sieve exchange mother liquor and washing water
+Content is 1.0 heavy %) add the 18ppm anionic polyacrylamide, stirred 1 minute, add 1ppm polymerization AlCl then
3, continue to stir after 2 minutes and leave standstill.Flocculent precipitate sinks rapidly.(2) supernatant liquid (turbidity is 15) is delivered to deep bed filter.Quartz sand is housed in the strainer, and bed height 500mm, quartz sand particle size are 1.1～2.0mm.Flow through behind the deep bed filter, the turbidity of clear liquid is 17.(3) clear liquid that step (2) is obtained carries out ion-exchange with being pumped into cationic exchange coloum, the Na of exchange back clear liquid
+Content is 0.4 heavy %.(4) in step (3) gained clear liquid, add NH
4Cl and HCl, the pH value to 3.0 of regulator solution, and to make the concentration of ammonium chloride be 12 heavy %, exchanges Na in the NaY molecular sieve filter cake of exchange back again with the NaY molecular sieve
+Content is 5.6 heavy %.And after the exchange solution exchange with fresh decationizing water configuration, Na in the molecular sieve filter cake
+Content is 5.2 heavy %.
Embodiment 3
The present embodiment explanation: after adopting method provided by the invention that molecular sieve exchange washing water is handled, the gained clear liquid can be mixed with molecular sieve exchange solution circulated and use.
Testing sequence is as follows: (1) is (its Na in the mixed solution of NaY molecular sieve exchange mother liquor and washing water
+Content is 1.0 heavy %) add the 10ppm cationic polyacrylamide, stirred 3 minutes, add 8ppm polymerization AlCl then
3, continue to stir after 2 minutes and leave standstill.Flocculent precipitate sinks rapidly.(2) supernatant liquid (turbidity is 12) is delivered to deep bed filter.Slag is housed in the strainer, and bed height 500mm, slag particle diameter are 1.0～2.0mm.Flow through behind the deep bed filter, the turbidity of clear liquid is 14.(3) clear liquid that step (2) is obtained carries out ion-exchange with being pumped into cationic exchange coloum, the Na of exchange back clear liquid
+Content is 0.6 heavy %.(4) in step (3) gained clear liquid, add NH
4Cl and HCl, the pH value to 3.0 of regulator solution, and to make the concentration of ammonium chloride be 12 heavy %, exchanges Na in the NaY molecular sieve filter cake of exchange back again with the NaY molecular sieve
+Content is 5.8 heavy %.And after the exchange solution exchange with fresh decationizing water configuration, Na in the molecular sieve filter cake
+Content is 5.0 heavy %.
Annotate: when measuring liquid turbidity, debug turbidometer as reference liquid with commercially available pure water.
Claims (6)
1, a kind of Y zeolite exchange washing water recycle method, it is characterized in that this method may further comprise the steps: (1) adds flocculation agent in molecular sieve exchange washing water, is stirred to form clear liquid and solid shape throw out; (2) separate above-mentioned clear liquid and solid shape throw out; (3) step (2) gained clear liquid passes through Zeo-karb; (4) step (3) gained clear liquid being mixed with molecular sieve exchange solution circulated uses.
2, according to the method for claim 1, the adding method that it is characterized in that the described flocculation agent of step (1) is as follows: add cationic polyacrylamide or anionic polyacrylamide in molecular sieve exchange washing water, its add-on is 5～20ppm, stirs at least 1 minute; Add polymerization AlCl then
3, its add-on is 1～10ppm, continues to be stirred to formation clear liquid and solid shape throw out.
3, according to the method for claim 2, the adding method that it is characterized in that the described flocculation agent of step (1) is as follows: add cationic polyacrylamide or anionic polyacrylamide in molecular sieve exchange washing water, its add-on is 8～15ppm, stirs at least 2 minutes; Add polymerization AlCl then
3, its add-on is 2～8ppm, continues to be stirred to formation clear liquid and solid shape throw out.
4,, it is characterized in that step (2) adopts deep bed filter separating step (1) gained clear liquid and solid shape throw out according to the method for claim 1.
5, according to the method for claim 4, it is characterized in that described deep bed filter with quartz sand or slag as weighting material, and their particle diameter is 0.7～2.0mm, bed height is 300～1000mm.
6, according to the method for claim 5, it is characterized in that described deep bed filter with quartz sand or slag as weighting material, and their particle diameter is 0.8～1.5mm, bed height is 400～900mm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021169241A CN1169731C (en) | 2002-04-26 | 2002-04-26 | Circular utilization of Y-type molecular sieve exchange washing water |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021169241A CN1169731C (en) | 2002-04-26 | 2002-04-26 | Circular utilization of Y-type molecular sieve exchange washing water |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1453220A CN1453220A (en) | 2003-11-05 |
| CN1169731C true CN1169731C (en) | 2004-10-06 |
Family
ID=29257055
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB021169241A Expired - Fee Related CN1169731C (en) | 2002-04-26 | 2002-04-26 | Circular utilization of Y-type molecular sieve exchange washing water |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1169731C (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102020288B (en) * | 2009-09-09 | 2012-10-03 | 北京思践通科技发展有限公司 | Ion exchange method for molecular sieve |
| JP5827572B2 (en) * | 2012-01-17 | 2015-12-02 | 住友化学株式会社 | Method for producing zeolite and method for producing ε-caprolactam |
| CN103523850B (en) * | 2013-10-21 | 2015-10-14 | 西南石油大学 | The application of molecular sieve in adsorption of polyacrylamide from wastewater |
| CN105540943B (en) | 2015-10-30 | 2018-03-20 | 中国石油化工股份有限公司 | The processing method of silicon-containing wastewater and the Application way of silicon-containing wastewater and molecular sieve preparation method |
| CN107010756B (en) * | 2017-05-04 | 2020-09-04 | 郑州大学 | Method for recycling and treating acidic wastewater generated by preparing titanium-silicon molecular sieve |
-
2002
- 2002-04-26 CN CNB021169241A patent/CN1169731C/en not_active Expired - Fee Related
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| Publication number | Publication date |
|---|---|
| CN1453220A (en) | 2003-11-05 |
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Granted publication date: 20041006 Termination date: 20110426 |