CN106938849A - The method that the molecular sieves of ZSM 5 are synthesized using waste and old molecular sieve catalyst - Google Patents
The method that the molecular sieves of ZSM 5 are synthesized using waste and old molecular sieve catalyst Download PDFInfo
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- CN106938849A CN106938849A CN201611144617.6A CN201611144617A CN106938849A CN 106938849 A CN106938849 A CN 106938849A CN 201611144617 A CN201611144617 A CN 201611144617A CN 106938849 A CN106938849 A CN 106938849A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/36—Pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
- C01B39/38—Type ZSM-5
- C01B39/40—Type ZSM-5 using at least one organic template directing agent
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
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- C01P2004/00—Particle morphology
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- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
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Abstract
The invention belongs to chemical field, it is related to Zeolite synthesis technology, and in particular to a kind of method that utilization spent catalyst synthesizes the molecular sieves of ZSM 5.This method reclaims spent catalyst, carries out determination of elemental analysis, and as a part for same type Zeolite synthesis raw material, the collosol intermixture that fresh feed is prepared into synthesis of molecular sieve is correspondingly added further according to proportioning, then the molecular sieves of ZSM 5 are synthesized by crystallization.The inventive method reclaims waste and old MTP catalyst, is circulated recycling, both reduces environmental pollution, raw material has been saved again, reduces the synthesis cost of molecular sieve.On the other hand, the crystal structure that spent catalyst still remains molecular sieve improves nucleation rate there is provided abundant nucleus, while reducing the particle size of sample, accelerates the crystallization process of molecular sieve.
Description
Technical field
The invention belongs to chemical field, it is related to Zeolite synthesis technology, and in particular to one kind utilizes spent catalyst synthesis
The method of ZSM-5 molecular sieve.
Background technology
Zeolite molecular sieve is important catalyst activity component or catalyst carrier in oil and chemical field.The U.S.
Mobil oil companies announced in USP3702886 in 1972 and invented after ZSM-5 zeolite molecular sieve, because it is with higher
Silica alumina ratio, unique three dimensional intersection pore passage structure and excellent hydrothermal stability, ZSM-5 molecular sieve is widely used in naphtha
Cracking, isomerization, aromatisation and methanol are converted in the reaction such as hydro carbons processed.With the fast development of chemical industry, it can all make every year
A large amount of molecular sieve catalysts are used, while also can the substantial amounts of waste and old molecular sieve catalyst of output.At present, these waste and old molecular sieve catalytics
Agent is treated as solid refuse processing mostly, and separately some is used for additives for building materials.These discarded molecular sieve catalytics
Agent can cause serious environmental pollution and waste of material.Research shows that decaying catalyst still remains the crystalline substance of moieties sieve
Body structure, it is contemplated that the crystal structure and chemical element composition of molecular sieve in itself, waste and old molecular sieve catalyst perhaps can turn into
The raw material of synthetic aluminosilicate product salt (mainly molecular sieve).So, the cost of material of synthesis of molecular sieve will be substantially reduced, thus
The environmental problem of initiation also will effectively be alleviated.It is also possible to assign the course of reaction environment friend based on molecular sieve catalytic
Good potentiality.
MTP techniques be have an exploitation of German LURGI Catalyst Production target product propylene is used as using ZSM-5 molecular sieve
New technology.Since first set MTP process units are after Shenhua Ningxia Coal Industry Group is driven successfully in the world, MTP techniques are caused
Academia and the extensive concern of industrial quarters.This has also triggered many researchs on improving MTP process efficiencies and catalyst efficiency
Discuss.At present, high silica ZSM-5 molecular sieve catalyst is proved to be a kind of excellent MTP catalyst of Performance comparision, is to ensure MTP
The key factor of high propylene yield in technical process.In addition, many researchs show that the diffusion of molecular sieve catalyst is also shadow
Ring the key factor of ZSM-5 molecular sieve catalyst catalytic performance in MTP reactions.Because the silica alumina ratio of ZSM-5 molecular sieve can be with
Realized by adjusting the sial composition of Primogel in building-up process, by reducing zeolite crystal size, to improve
The diffusion of ZSM-5 molecular sieve catalyst turns into the difficult point and focus of research MTP catalyst.
The A of Chinese patent CN 102001680 disclose a kind of method for preparing nano-ZSM-5 molecular sieve, and it uses no mould
Plate agent method prepares mixed solution and agitation and dropping method prepares mixed glue solution two-step method and prepares presoma, by crystallization, filtering, dries
And roasting, granularity is finally given for 50~100nm molecular sieves.The B of patent CN 101428818 disclose a kind of nano-ZSM-5 point
The synthetic method of son sieve, it is oriented to the structure directing of ZSM-23 molecular screen by being introduced into ZSM-5 molecular sieve precursor liquid
Agent --- right button isopropylamine, so as to disturb established nucleus growth, reaches the purpose of synthesis nano-ZSM-5 molecular sieve.Patent
The B's of CN 101182004 discloses a kind of preparation method of nano molecular sieve, its to molecular sieve precursor liquid add hydrocarbon component and
Surfactant, obtains the oily super compatibilization system of bag fused mass, and effective restriction molecule sieves crystal growth, then by crystallization, drying and
Roasting obtains nano-class molecular sieve.Therefore under the situation that current ZSM-5 molecular sieve application field constantly expands, with cheap, letter
Just method synthesis ZSM-5 molecular sieve research is with very high commercial value.And waste and old molecular sieve catalyst is typically only capable to discard,
Environment is not only polluted, the waste of raw material is also resulted in.
The content of the invention
The purpose of the present invention is to make up the deficiencies in the prior art to synthesize ZSM-5 molecules using spent catalyst there is provided one kind
The method of sieve, can reduce environmental pollution, economize in raw materials, reduce the synthesis cost of molecular sieve, improve nucleation rate,
While reducing the particle size of sample, the crystallization process of acceleration molecular sieve.
The present invention using spent catalyst synthesize ZSM-5 molecular sieve method be：Spent catalyst is reclaimed, as
ZSM-5 molecular sieve synthesis material is continuing with, including step：
(1) spent catalyst is reclaimed, wherein SiO is analyzed2、Al2O3、Na2O、OH-Content；
(2) according to the content of each component in spent catalyst, add in proportion silicon source, silicon source, template, NaOH and
Water, is configured to synthesize the gel mixture of ZSM-5 molecular sieve；
By step (2) in obtained ZSM-5 molecular sieve gel mixture be fitted into the reactor of polytetrafluoroethyllining lining,
Crystallization obtains corresponding ZSM-5 molecular sieve crystallization liquid；
By step (3) in obtained ZSM-5 molecular sieve crystallization liquid separated, washed, obtain ZSM-5 molecular sieve solid,
The former powder of ZSM-5 molecular sieve that ZSM-5 molecular sieve solid is obtained through drying, roasting；
Preferably：One or more of the silicon source in Ludox, waterglass, tetraethyl orthosilicate or silica gel.
Preferably：The one or more in sodium metaaluminate, the thin water aluminium of plan or aluminum sulfate of source of aluminium.
Preferably：The aluminosilicate gels mol ratio is SiO2：Al2O3：Na2O：H2O=50~400：1：10~35：
2000~5400.
Preferably：Template is tetraethyl ammonium hydroxide, TPAOH, n-butylamine, 4-propyl bromide or three
The one or more of monoethanolamine；And template and SiO in aluminosilicate gels2Mass ratio be 0.02~0.45.
Preferably：The crystallization condition is to be kept for 10~48 hours at a temperature of 6~120 DEG C, is warming up to 120~180 DEG C,
Keep again 10~36 hours, obtain ZSM-5 molecular sieve crystallization liquid.
The device have the advantages that：
On the one hand the method for the invention can effectively shorten the generated time of synthesis ZSM-5 molecular sieve；Urged due to waste and old
Agent remains the crystal structure of molecular sieve there is provided abundant nucleus, improves nucleation rate, reduces the particle size of sample
While, accelerate the crystallization process of molecular sieve；On the other hand waste and old MTP catalyst is recycled, can be effectively
Production cost is reduced, the pollution to environment is also reduced.
Brief description of the drawings
Fig. 1 is (a) comparative example 1, (b) comparative example 2, (c) embodiment 1, the stereoscan photograph of (d) embodiment 2；
Fig. 2 is (a) comparative example 1, (b) comparative example 2, (c) embodiment 1, the XRD of (d) embodiment 2.
Embodiment
With reference to embodiment, the invention will be further described, but protection scope of the present invention is not limited solely to implement
Example.
Embodiment 1
7.04g NaOH is added in 130.2g distilled water, stirred to being completely dissolved, by 5g spent catalyst
(dioxide-containing silica is 88.15%, and alumina content is 0.448%) to be added in above-mentioned solution, and stirring, will to being completely dissolved
1.28g sodium metaaluminate, which is added in above-mentioned solution, to be stirred to being completely dissolved.It is under agitation that 145g Ludox is slow
It is added drop-wise in above-mentioned mixed solution and forms aluminosilicate gels A；A certain amount of TPAOH is weighed, wherein add four
The mass ratio of propyl group ammonium hydroxide and silica in aluminosilicate gels is 0.25, and above-mentioned TPAOH is dissolved in
Stirred in 30.8g deionized water to being completely dissolved, obtain mixed solution B, solution B is slowly added into A under agitation coagulates
Make to be well mixed in glue, finally mixture is transferred in the stainless steel crystallizing kettle of teflon lined, 80 are warming up to from normal temperature
DEG C, then crystallization 36 hours under the conditions of 80 DEG C；120 DEG C are warming up to again, crystallization 36 hours under the conditions of 120 DEG C；Product is through dividing
From obtaining the former powder of ZSM-5 molecular sieve after separating, washing, drying, roasting；
Comparative example 1
7.04g NaOH is added in 130.2g distilled water, stirs to being completely dissolved, 1.3g sodium metaaluminate is added
Enter into above-mentioned solution to stir to being completely dissolved.150g Ludox is slowly dropped to above-mentioned mixed solution under agitation
Middle formation aluminosilicate gels A；A certain amount of TPAOH is weighed, wherein the TPAOH and sial that add
The mass ratio of silica is 0.25 in hydrochlorate gel, and above-mentioned TPAOH is dissolved in 30.8g deionized water and stirred
Mix to being completely dissolved, obtain mixed solution B, be slowly added to solution B to make to be well mixed in A gels under agitation, finally
Mixture is transferred in the stainless steel crystallizing kettle of teflon lined, 80 DEG C are warming up to from normal temperature, then under the conditions of 80 DEG C
Crystallization 36 hours；120 DEG C are warming up to again, crystallization 36 hours under the conditions of 120 DEG C；After product separating, washing, drying, roasting
Obtain the former powder of ZSM-5 molecular sieve；
Embodiment 2
7.04g NaOH is added in 130.2g distilled water, stirred to being completely dissolved, by 10g spent catalyst
(dioxide-containing silica is 88.15%, and alumina content is 0.448%) to be added in above-mentioned solution, and stirring, will to being completely dissolved
1.25g sodium metaaluminate, which is added in above-mentioned solution, to be stirred to being completely dissolved.It is under agitation that 140g Ludox is slow
It is added drop-wise in above-mentioned mixed solution and forms aluminosilicate gels A；A certain amount of TPAOH is weighed, wherein add four
The mass ratio of propyl group ammonium hydroxide and silica in aluminosilicate gels is 0.25, and above-mentioned TPAOH is dissolved in
Stirred in 30.8g deionized water to being completely dissolved, obtain mixed solution B, solution B is slowly added into A under agitation coagulates
Make to be well mixed in glue, finally mixture is transferred in the stainless steel crystallizing kettle of teflon lined, 80 are warming up to from normal temperature
DEG C, then crystallization 36 hours under the conditions of 80 DEG C；120 DEG C are warming up to again, crystallization 36 hours under the conditions of 120 DEG C；Product is through dividing
From obtaining the former powder of ZSM-5 molecular sieve after separating, washing, drying, roasting；
Comparative example 2
7.04g NaOH is added in 130.2g distilled water, stirred to being completely dissolved, after 10g regeneration treatments
(dioxide-containing silica is 88.15% to spent catalyst, and alumina content is 0.448%) to be added in above-mentioned solution, and stirring is extremely
It is completely dissolved, 1.25g sodium metaaluminate is added in above-mentioned solution and stirred to being completely dissolved.Under agitation by 140g's
Ludox, which is slowly dropped in above-mentioned mixed solution, forms aluminosilicate gels A；A certain amount of TPAOH is weighed, its
The mass ratio of silica is 0.25 in the TPAOH and aluminosilicate gels of middle addition, by above-mentioned tetrapropyl hydrogen-oxygen
Change ammonium to be dissolved in 30.8g deionized water and stirring to being completely dissolved, obtain mixed solution B, it is under agitation that solution B is slow
Add makes to be well mixed in A gels, finally mixture is transferred in the stainless steel crystallizing kettle of teflon lined, from normal temperature liter
Temperature is to 80 DEG C, then crystallization 36 hours under the conditions of 80 DEG C；120 DEG C are warming up to again, crystallization 36 hours under the conditions of 120 DEG C；Production
Thing obtains the former powder of ZSM-5 molecular sieve after separating separating, washing, drying, roasting；
Above-described embodiment and the product stereoscan photograph and XRD of comparative example are as shown in Figure 1 and Figure 2.
Finally it should be noted that：Above example only not limits technology described in the invention to illustrate the present invention
Scheme, therefore, although this specification with reference to each above-mentioned embodiment to present invention has been detailed description, this
Field it is to be appreciated by one skilled in the art that still can be modified to the present invention or equivalent, and all do not depart from this
The technical scheme of the spirit and scope of invention and its improvement, it all should cover in scope of the presently claimed invention.
Claims (6)
1. a kind of method that utilization spent catalyst synthesizes ZSM-5 molecular sieve, it is characterized in that：
Spent catalyst is reclaimed, is continuing with as ZSM-5 molecular sieve synthesis material, including step：
(1) spent catalyst is reclaimed, wherein SiO is analyzed2、Al2O3、Na2O、OH-Content；
(2), according to the content of each component in spent catalyst, silicon source, silicon source, template, NaOH, He Shui are added in proportion,
It is configured to synthesize the gel mixture of ZSM-5 molecular sieve；
By step (2) in obtained ZSM-5 molecular sieve gel mixture be fitted into the reactor of polytetrafluoroethyllining lining, crystallization
Obtain corresponding ZSM-5 molecular sieve crystallization liquid；
By step (3) in obtained ZSM-5 molecular sieve crystallization liquid separated, washed, obtain ZSM-5 molecular sieve solid, will
The former powder of ZSM-5 molecular sieve that ZSM-5 molecular sieve solid is obtained through drying, roasting.
2. the method that utilization spent catalyst according to claim 1 synthesizes ZSM-5 molecular sieve, it is characterized in that：The silicon
One or more of the source in Ludox, waterglass, tetraethyl orthosilicate or silica gel.
3. the method that utilization spent catalyst according to claim 1 synthesizes ZSM-5 molecular sieve, it is characterized in that：The aluminium
The one or more in sodium metaaluminate, the thin water aluminium of plan or aluminum sulfate in source.
4. the method that utilization spent catalyst according to claim 1 synthesizes ZSM-5 molecular sieve, it is characterized in that：The silicon
Aluminate gel mol ratio is SiO2：Al2O3：Na2O：H2O=50~400：1：10~35：2000~5400.
5. the method that utilization spent catalyst according to claim 1 synthesizes ZSM-5 molecular sieve, it is characterized in that：The mould
Plate agent is one kind or many of tetraethyl ammonium hydroxide, TPAOH, n-butylamine, 4-propyl bromide or triethanolamine
Kind；And template and SiO in aluminosilicate gels2Mass ratio be 0.02~0.45.
6. the method that utilization spent catalyst according to claim 1 synthesizes ZSM-5 molecular sieve, it is characterized in that：The crystalline substance
Change condition is to be kept for 10~48 hours at a temperature of 6~120 DEG C, is warming up to 120~180 DEG C, then is kept for 10~36 hours, is obtained
ZSM-5 molecular sieve crystallization liquid.
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109225320A (en) * | 2018-11-05 | 2019-01-18 | 宁夏大学 | A kind of MFI structure deposed molecular sieve crystallization regeneration method |
| CN109485064A (en) * | 2018-12-10 | 2019-03-19 | 卓悦环保新材料（上海）有限公司 | The method of useless MTP catalyst preparation modenite and the application of useless MTP catalyst |
| CN109647329A (en) * | 2019-01-29 | 2019-04-19 | 大连理工大学盘锦产业技术研究院 | A kind of binder free composite molecular screen preparation method and its application in oil product absorption desulfurization |
| CN110128163A (en) * | 2019-06-26 | 2019-08-16 | 中南大学 | A method of porous cordierite ceramics material is prepared using waste catalyst |
| CN111072046A (en) * | 2019-12-26 | 2020-04-28 | 河北欣芮再生资源利用有限公司 | Method for preparing ZSM-5 molecular sieve by using catalytic cracking waste catalyst |
| CN111302355A (en) * | 2020-02-20 | 2020-06-19 | 山东齐鲁华信高科有限公司 | Preparation method of mesoporous Fe-Beta molecular sieve |
| CN111330537A (en) * | 2020-03-05 | 2020-06-26 | 国家能源集团宁夏煤业有限责任公司 | Heavy metal adsorbent and preparation method and application thereof |
| CN111744539A (en) * | 2019-03-28 | 2020-10-09 | 中国石油化工股份有限公司 | Preparation method of catalyst used in method for preparing ethylbenzene by benzene-ethylene gas phase alkylation |
| CN111744545A (en) * | 2019-03-28 | 2020-10-09 | 中国石油化工股份有限公司 | Preparation method of catalyst used in method for preparing ethylbenzene by benzene-ethylene liquid phase alkylation |
| CN112093809A (en) * | 2020-08-13 | 2020-12-18 | 国家能源集团宁夏煤业有限责任公司 | Waste catalyst treatment method, HZSM-5 molecular sieve, and preparation method and application thereof |
| CN112090394A (en) * | 2020-08-13 | 2020-12-18 | 国家能源集团宁夏煤业有限责任公司 | Adsorbent, preparation method thereof and treatment method of organic wastewater |
| CN112604651A (en) * | 2020-12-18 | 2021-04-06 | 湖北润驰环保科技有限公司 | Method for preparing high-efficiency desulfurizer by using waste molecular sieve catalyst and waste zinc oxide desulfurizer as raw materials |
| CN112661168A (en) * | 2019-10-15 | 2021-04-16 | 国家能源投资集团有限责任公司 | Lamellar ZSM-5 molecular sieve and preparation method and application thereof |
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| CN109225320A (en) * | 2018-11-05 | 2019-01-18 | 宁夏大学 | A kind of MFI structure deposed molecular sieve crystallization regeneration method |
| CN109485064A (en) * | 2018-12-10 | 2019-03-19 | 卓悦环保新材料（上海）有限公司 | The method of useless MTP catalyst preparation modenite and the application of useless MTP catalyst |
| CN109647329A (en) * | 2019-01-29 | 2019-04-19 | 大连理工大学盘锦产业技术研究院 | A kind of binder free composite molecular screen preparation method and its application in oil product absorption desulfurization |
| CN111744539A (en) * | 2019-03-28 | 2020-10-09 | 中国石油化工股份有限公司 | Preparation method of catalyst used in method for preparing ethylbenzene by benzene-ethylene gas phase alkylation |
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| CN110128163A (en) * | 2019-06-26 | 2019-08-16 | 中南大学 | A method of porous cordierite ceramics material is prepared using waste catalyst |
| CN112661168A (en) * | 2019-10-15 | 2021-04-16 | 国家能源投资集团有限责任公司 | Lamellar ZSM-5 molecular sieve and preparation method and application thereof |
| CN112661168B (en) * | 2019-10-15 | 2023-02-24 | 国家能源投资集团有限责任公司 | Lamellar ZSM-5 molecular sieve and preparation method and application thereof |
| CN111072046A (en) * | 2019-12-26 | 2020-04-28 | 河北欣芮再生资源利用有限公司 | Method for preparing ZSM-5 molecular sieve by using catalytic cracking waste catalyst |
| CN111302355A (en) * | 2020-02-20 | 2020-06-19 | 山东齐鲁华信高科有限公司 | Preparation method of mesoporous Fe-Beta molecular sieve |
| CN111330537A (en) * | 2020-03-05 | 2020-06-26 | 国家能源集团宁夏煤业有限责任公司 | Heavy metal adsorbent and preparation method and application thereof |
| CN112093809A (en) * | 2020-08-13 | 2020-12-18 | 国家能源集团宁夏煤业有限责任公司 | Waste catalyst treatment method, HZSM-5 molecular sieve, and preparation method and application thereof |
| CN112090394A (en) * | 2020-08-13 | 2020-12-18 | 国家能源集团宁夏煤业有限责任公司 | Adsorbent, preparation method thereof and treatment method of organic wastewater |
| CN112090394B (en) * | 2020-08-13 | 2023-08-22 | 国家能源集团宁夏煤业有限责任公司 | Adsorbent, preparation method thereof and treatment method of organic wastewater |
| CN112604651A (en) * | 2020-12-18 | 2021-04-06 | 湖北润驰环保科技有限公司 | Method for preparing high-efficiency desulfurizer by using waste molecular sieve catalyst and waste zinc oxide desulfurizer as raw materials |
| CN112604651B (en) * | 2020-12-18 | 2023-06-09 | 湖北润驰环保科技有限公司 | Method for preparing efficient desulfurizing agent by using waste molecular sieve catalyst and waste zinc oxide desulfurizing agent as raw materials |
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