CN105126903A - Recycle method of catalyst fine powder obtained by preparation of olefin from waste and old methanol - Google Patents

Recycle method of catalyst fine powder obtained by preparation of olefin from waste and old methanol Download PDF

Info

Publication number
CN105126903A
CN105126903A CN201510456094.8A CN201510456094A CN105126903A CN 105126903 A CN105126903 A CN 105126903A CN 201510456094 A CN201510456094 A CN 201510456094A CN 105126903 A CN105126903 A CN 105126903A
Authority
CN
China
Prior art keywords
catalyst
waste
fine powder
methanol
olefin
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201510456094.8A
Other languages
Chinese (zh)
Inventor
狄春雨
李晓峰
梁光华
王龙
王平
李志宏
窦涛
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shenzhen science and Technology Co., Ltd.
Original Assignee
Taiyuan Dacheng Huanneng Chemical Technology Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Taiyuan Dacheng Huanneng Chemical Technology Co Ltd filed Critical Taiyuan Dacheng Huanneng Chemical Technology Co Ltd
Priority to CN201510456094.8A priority Critical patent/CN105126903A/en
Publication of CN105126903A publication Critical patent/CN105126903A/en
Pending legal-status Critical Current

Links

Classifications

    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/40—Ethylene production

Abstract

The invention discloses a recycle method of catalyst fine powder obtained by preparation of an olefin from waste and old methanol. The recycle method comprises carrying out roasting on catalyst fine powder obtained by preparation of an olefin from waste and old methanol to remove carbon deposit, putting the roasted catalyst fine powder on an upper part of a crystallization kettle, putting deionized water and an organic amine template on the lower part, carrying out crystallization, mixing the fine powder subjected to crystallization, deionized water, SAPO-34 molecular sieve powder, a binder and a matrix to obtain slurry, carrying out stirring, grinding and ageing, and carrying out spray molding and roasting to obtain catalyst microspheres for preparation of olefin from waste and old methanol. The recycle method has the advantages of high catalytic activity after regeneration, good selectivity and high strength.

Description

The reuse method of waste and old methanol-to-olefin catalyst fine powder
Technical field
The present invention relates to a point a kind of reuse method of waste and old methanol-to-olefins (MTO) catalyst fines.
Background technology
Methanol-to-olefins technology (hereinafter referred to as MTO technology) is the high-end core technology in world energy sources chemical field.The methyl alcohol that it is made with coal or natural gas, for raw material, becomes important industrial chemicals-light olefin (ethene and propylene) through MTO technology process change, and then derives numerous olefines chemical products.For the national conditions of China's " rich coal of oil starvation weak breath ", this realizes with the revolutionary industrial technology of coal petroleum replacing.Become the core technology of national great energy strategy.But the core of this type of technology is catalyst, because methanol to olefins reaction carries out in a fluidized bed reactor, therefore, the activity of catalyst and wearability are particularly important.
Numerous microspherical catalyst preparation method that patent describes for MTO reaction.Up to the present, the SAPO-34 molecular sieve with CHA topological structure is considered to the optimum activity component of MTO catalysts, and wherein US Patent No. 4440871 and US5279810 all describe SAPO-34 molecular sieve preparation method.
The molecular sieve molded method of SAPO-34 that it is carrier that US4987110 patent discloses with kaolin, Ludox is binding agent, CN102284302A patent also discloses a kind of methanol-to-olefin catalyst method for preparing microsphere, and Dalian Chemiclophysics Inst., Chinese Academy of Sciences patent CN101121148.2008 discloses a kind of direct forming method of fluidized reaction catalyst containing molecular sieve.In order to improve the intensity of MTO catalyst further, domestic and international researcher has carried out again a large amount of exploratory experiments, such as, US7214844B2.2007 patent discloses the forming method improving MTO catalyst scuff resistance, and the method reduces the abrasion index of preformed catalyst to greatest extent by optimizing each component proportion in preparation; In the patent CN1341584A.2002 of Praxair Technology, Inc's application, disclose the scuff resistance that a kind of method by reducing active component consumption improves catalyst, the shortcoming of the method is to significantly limit catalyst usefulness in the reaction; Same pointing out in US Patent No. 20070249885A1.2007, by burin-in process certain hour under mild conditions after binding agent, carrier and molecular sieve mixed pulp, can improve the scuff resistance of preformed catalyst effectively.Dalian Inst of Chemicophysics, Chinese Academy of Sciences patent CN101121531.2008 and US Patent No. 6153552A points out that in the molecular sieve molded slurries of SAPO-34, add phosphorus source both can improve catalyst strength, also can improve catalytic performance.
But it is carry out in the recirculating fluidized bed with successive reaction-regeneration that the technical characterstic of methanol to olefins reaction determines reaction, there is the physical process that frequent impact, reunion etc. are complicated in solid particle behavior.Constantly catalyst fines can be produced in whole process, if these catalyst fines discarded will bring serious problems to environmental protection, catalyst is expensive simultaneously, if the recycling of these catalyst can be realized, the environmental problem that catalyst fines brings can be solved on the one hand, make it to turn waste into wealth; Catalyst cost can be reduced on the other hand, and then reduce methanol-to-olefins cost.
Chinese patent CN1207097C reports the catalyst fines and part SAPO-34 molecular sieve that utilize component loops fluidized reaction to reclaim, binding agent, carrier, peptizing agent is mixed into homogeneous slurry, then spray-dried technique prepares methanol-to-olefin catalyst, be of value to by the recovery of attrition particles and application and waste is minimized, thus reduce environment and economy restriction problem, but do not consider in this patent in catalyst fines due to containing carbon distribution, the compositions such as binding agent, and these compositions distributional difference in catalyst fines is larger, not treated direct and SAPO-34 molecular sieve, binding agent, the shaping obtained catalyst of the mixed atomizings such as carrier cannot reach raw catalyst intensity and catalytic performance.
Take into account the problems referred to above in patent CN102389834A, catalyst fines is first removed carbon distribution through roasting and catalyst breakage is realized molecular sieve and is separated with binding agent, matrix etc., the materials such as the binding agent that separation is peeled off and medium carrier use as the filling in raw catelyst, then the pure auxiliary agent such as SAPO-34 molecular sieve, binding agent, filler to be mixed with the catalyst fines processed and shaping, make the catalyst fines of recovery realize recycling by this method, thus reduce catalyst cost.
Summary of the invention
After the object of the present invention is to provide a kind of regeneration, catalytic activity is high, selective good, the reuse method of the waste and old methanol-to-olefin catalyst fine powder that intensity is high.
Method of the present invention, comprises the following steps:
(1) by waste and old methanol-to-olefin catalyst fine powder, its size distribution, D50 is 20 ~ 50 μm, and D90 is 50 ~ 80 μm, at 450 DEG C ~ 650 DEG C roasting 1 ~ 5h to remove the 3 ~ 5wtw% carbon distribution in catalyst fines;
(2) catalyst fines after roasting is placed in crystallizing kettle top, puts deionized water and organic amine template in reactor bottom, 120 ~ 200 DEG C, crystallization 6 ~ 36h under pressure condition;
(3) fine powder after crystallization and deionized water, SAPO-34 molecular sieve powder, binding agent, matrix are mixed to get slurries, through stirring, grinding, then slurries ageing 6 ~ 36h, preferably 8 ~ 20h, then prepare methanol-to-olefin catalyst microballoon through spray shaping, 580 ~ 700 DEG C of roasting 2 ~ 8h.
Step described above (1) catalyst is SAPO-34 molecular sieve catalyst, and as the production piece that Baofeng, Ningxia energy group company provides, catalyst molar ratio is composed as follows: SiO 2: Al 2o 3: P 2o 5: C=0.1 ~ 0.5:1.0:0.5 ~ 0.9:0.05 ~ 0.19.
Step as above (2) described in organic amine template be triethylamine, morpholine or di-n-propylamine, its use amount is 20% ~ 80% of catalyst fines quality; The use amount of described deionized water is 10% ~ 90% of catalyst fines quality.
Step as above (3) described in the use amount of SAPO-34 molecular sieve powder (D50 is 1 ~ 3 μm, and D90 is 4 ~ 6 μm) be 5 ~ 15% of catalyst fines quality.
Step as above (3) described in binding agent be Alumina gel or Ludox, preferred Alumina gel, its addition is 8 ~ 15% of catalyst fines quality.
Step as above (3) described in matrix be kaolin or bentonite, preferred kaolin, its addition is 5 ~ 30% of catalyst fines quality.
Step as above (3) described in slurries the mass content of solid be 30 ~ 55%, grinding rear slurry ageing 6 ~ 36h, preferably 8 ~ 20h.
Step as above (3) described in spraying dry adopt centrifugal spray drying device, sprayer inlet temperature is 350 ~ 550 DEG C, and outlet temperature is 110 ~ 190 DEG C.
On the other hand, the invention provides a kind of molecular sieve catalyst obtained according to preceding method.
On the other hand, the invention provides the application of a kind of previous molecular sieve catalyst in methanol to olefins reaction, its reaction condition is: reaction temperature 480 DEG C, normal pressure, liquid air speed 2h -1, material benzenemethanol mass fraction is 95%.
Tool of the present invention has the following advantages:
Method of the present invention makes waste and old MTO catalyst fines achieve recycling, thus significantly reduces Catalyst Production cost, and gained catalyst maintains good catalytic activity, selective and intensity.
Detailed description of the invention
Embodiment 1
(1) take 200 grams of waste and old methanol-to-olefin catalyst, size distribution is D50 is 25 μm, and D90 is 50 μm, and catalyst fines is the production piece provided by Baofeng, Ningxia energy group company, composition (mol ratio) SiO 2: Al 2o 3: P 2o 5: C=0.2:1.0:0.6:0.13, fine powder was 550 DEG C of roastings 2.5 hours;
(2) catalyst fines after roasting is put into high pressure crystallizing kettle top, put into 120 grams of deionized waters and 80 grams of triethylamines in reactor bottom, from lower 170 DEG C of crystallization of pressure condition 24 hours;
(3) crystallization terminate after by being separated the solid dispersal that obtains in 75 grams of deionized waters, add 20 grams of SAPO-34 molecular sieves (referenced patent CN102942190A embodiment 3 is made by oneself), 25 grams of Alumina gel (Al successively 2o 3mass fraction is 21%), 23 grams of kaolin, through stirring, grinding, then ageing 10 hours, more shaping (inlet temperature is 450 DEG C through centrifugal spray, outlet temperature is 130 DEG C), 600 DEG C of roastings, 4 hours obtained methanol-to-olefin catalyst microballoons, be labeled as G1.
Embodiment 2
(1) (size distribution is D50 is 35 μm, and D90 is 58 μm, fine powder composition (mol ratio) SiO to take 260 grams of catalyst fines 2: Al 2o 3: P 2o 5: C=0.3:1.0:0.7:0.15, catalyst fines is the production piece provided by Baofeng, Ningxia energy group company) 650 DEG C of roastings 1 hour;
(2) catalyst fines after roasting is put into high pressure crystallizing kettle top, put into 100 grams of deionized waters and 68 grams of morpholines in reactor bottom, from lower 180 DEG C of crystallization of pressure condition 24 hours;
(3) crystallization terminate after by being separated the solid dispersal that obtains in 90 grams of deionized waters, add 23 grams of SAPO-34 molecular sieves (referenced patent CN101284246A embodiment 1), 30 grams of Alumina gel (Al successively 2o 3mass fraction is 21%), 36 grams of kaolin, through stirring, grinding, then ageing 15 hours, more shaping (inlet temperature is 380 DEG C through centrifugal spray, outlet temperature is 110 DEG C), 650 DEG C of roastings, 3 hours obtained methanol-to-olefin catalyst microballoons, be labeled as G2.
Embodiment 3
(1) (size distribution is D50 is 37 μm, and D90 is 65 μm, fine powder composition (mol ratio) SiO to take 320 grams of catalyst fines 2: Al 2o 3: P 2o 5: C=0.3:1.0:0.8:0.12, catalyst fines is the production piece provided by Baofeng, Ningxia energy group company) 500 DEG C of roastings 5 hours;
(2) catalyst fines after roasting is put into high pressure crystallizing kettle top, put into 110 grams of deionized waters and 160 grams of di-n-propylamines in reactor bottom, from lower 190 DEG C of crystallization of pressure condition 18 hours;
(3) crystallization will be separated the solid dispersal that obtains in 90 grams of deionized waters after terminating, add 36 grams of SAPO-34 molecular sieve (bibliography: Liu Hongxing successively, Xie Ku, Zhang Chengfang etc. the synthesis I of fine grain SAPO-34 molecular sieve: chemical synthesis [J]. East China University of Science's journal, 2003,29 (5): 527-530), 60 grams of Alumina gel (Al 2o 3mass fraction is 21%), 43 grams of kaolin, through stirring, grinding, then ageing 20 hours, more shaping (inlet temperature is 530 DEG C through centrifugal spray, outlet temperature is 170 DEG C), 680 DEG C of roastings, 2 hours obtained methanol-to-olefin catalyst microballoons, be labeled as G3.
Embodiment 4
(1) (size distribution is D50 is 38 μm, and D90 is 75 μm, fine powder composition (mol ratio) SiO to take 270 grams of catalyst fines 2: Al 2o 3: P 2o 5: C=0.3:1.0:0.8:0.15 catalyst fines is the production piece provided by Baofeng, Ningxia energy group company) 650 DEG C of roastings 1 hour;
(2) catalyst fines after roasting is put into high pressure crystallizing kettle top, put into 80 grams of deionized waters and 150 grams of triethylamines in reactor bottom, from the lower 200 DEG C of crystallization 6h of pressure condition;
(3) crystallization terminate after by being separated the solid dispersal that obtains in 65 grams of deionized waters, add 50 grams of SAPO-34 molecular sieves (referenced patent CN103420388A embodiment 1), 78 grams of Alumina gel (Al successively 2o 3mass fraction is 21%), 35 grams of kaolin, through stirring, grinding, then ageing 17 hours, more shaping (inlet temperature is 350 DEG C through centrifugal spray, outlet temperature is 110 DEG C), 600 DEG C of roastings, 4 hours obtained methanol-to-olefin catalyst microballoons, be labeled as G4.
Embodiment 5
(1) (size distribution is D50 is 45 μm, and D90 is 75 μm, fine powder composition (mol ratio) SiO to take 280 grams of catalyst fines 2: Al 2o 3: P 2o 5: C=0.2:1.0:0.7:0.16, catalyst fines is the production piece provided by Baofeng, Ningxia energy group company) 580 DEG C of roastings 4 hours;
(2) catalyst fines after roasting is put into high pressure crystallizing kettle top, put into 160 grams of deionized waters and 80 grams of triethylamines in reactor bottom, from lower 190 DEG C of crystallization of pressure condition 16 hours;
(3) crystallization terminate after by being separated the solid dispersal that obtains in 85 grams of deionized waters, add 36 grams of SAPO-34 molecular sieves (referenced patent CN101293660A embodiment 1), 40 grams of Ludox (SiO successively 2mass fraction is 40%), 30 grams of kaolin, through stirring, grinding, then ageing 15 hours, centrifugal spray is shaping, and (inlet temperature is 460 DEG C, outlet temperature is 140 DEG C), 700 DEG C of roastings, 2 hours obtained methanol-to-olefin catalyst microballoons, be labeled as G5.
Comparative example 1
200 grams of SAPO-34 molecular sieves (referenced patent CN102942190A embodiment 3 is made by oneself) are scattered in 120 grams of deionized waters, add 75 grams of Alumina gel (Al 2o 3mass fraction is 21%), 180 grams of kaolin, through stirring, grinding, then ageing 12 hours, again through centrifugal spray shaping (inlet temperature is 380 DEG C, and outlet temperature is 120 DEG C), 650 DEG C of roastings, 4 hours obtained methanol-to-olefin catalyst microballoons, be labeled as H-1.
Molecular sieve catalyst is evaluated
Adopt fixed bed catalyst evaluating apparatus, respectively gained catalyst and raw catalyst in embodiment are taken 2.0 grams and put into reactor constant temperature zone, logical nitrogen activation 0.5 hour at 500 DEG C, then 450 DEG C are cooled to, material benzenemethanol (mass fraction 95%) enters reactor through micro pump and reacts, and methanol weight air speed is 3h -1, reaction afterproduct adopts off-line gas-chromatography to analyze, and illustrating that methanol conversion has not been 100%, now stopping reaction when dimethyl ether being detected.Catalyst abrasion index adopts standard Attrition indexer to record.Concrete result of the test is see table 1.
Table 1
H-1 G-1 G-2 G-3 G-4 G-5
Methanol conversion (%) 100 100 100 100 100 100
Ethene+Propylene Selectivity (%) 83.54 83.90 84.13 83.75 83.40 83.97
Life-span (min) 80 85 80 75 80 85
Abrasion index (%/hr) 0.88 0.75 1.02 0.84 0.67 0.86

Claims (14)

1. a reuse method for waste and old methanol-to-olefin catalyst fine powder, is characterized in that comprising the following steps:
By waste and old methanol-to-olefin catalyst fine powder, its size distribution, D50 is 20 ~ 50 μm, and D90 is 50 ~ 80 μm, at 450 DEG C ~ 650 DEG C roasting 1 ~ 5h to remove the 3 ~ 5wt% carbon distribution in catalyst fines;
(2) the catalyst fines after roasting is placed in crystallizing kettle top, puts deionized water and organic amine template in reactor bottom, 120 ~ 200 DEG C, crystallization 6 ~ 36h under pressure condition;
Fine powder after crystallization and deionized water, SAPO-34 molecular sieve powder, binding agent, matrix are mixed to get slurries, through stirring, grinding, then slurries ageing 6 ~ 36h, preferably 8 ~ 20h, then prepare methanol-to-olefin catalyst microballoon through spray shaping, 580 ~ 700 DEG C of roasting 2 ~ 8h.
2. the reuse method of a kind of waste and old methanol-to-olefin catalyst fine powder as claimed in claim 1, is characterized in that described step (1) catalyst is SAPO-34 molecular sieve catalyst.
3. the reuse method of a kind of waste and old methanol-to-olefin catalyst fine powder as claimed in claim 2, is characterized in that described SAPO-34 molecular sieve catalyst is that catalyst molar ratio consists of SiO 2: Al 2o 3: P 2o 5: C=0.1 ~ 0.5:1.0:0.5 ~ 0.9:0.05 ~ 0.19.
4. the reuse method of a kind of waste and old methanol-to-olefin catalyst fine powder as claimed in claim 1, it is characterized in that organic amine template is triethylamine, morpholine or di-n-propylamine described in described step is (2), its use amount is 20% ~ 80% of catalyst fines quality; The use amount of described deionized water is 10% ~ 90% of catalyst fines quality.
5. the reuse method of a kind of waste and old methanol-to-olefin catalyst fine powder as claimed in claim 1, it is characterized in that SAPO-34 molecular sieve powder use amount is 5 ~ 15% of catalyst fines quality described in described step (3), its D50 is 1 ~ 3 μm, and D90 is 4 ~ 6 μm.
6. the reuse method of a kind of waste and old methanol-to-olefin catalyst fine powder as claimed in claim 1, it is characterized in that binding agent is Alumina gel or Ludox described in described step (3), its addition is 8 ~ 15% of catalyst fines quality.
7. the reuse method of a kind of waste and old methanol-to-olefin catalyst fine powder as claimed in claim 6, is characterized in that binding agent is Alumina gel described in described step (3).
8. the reuse method of a kind of waste and old methanol-to-olefin catalyst fine powder as claimed in claim 1, it is characterized in that matrix is kaolin or bentonite described in described step (3), its addition is 5 ~ 30% of catalyst fines quality.
9. the reuse method of a kind of waste and old methanol-to-olefin catalyst fine powder as claimed in claim 8, is characterized in that matrix is kaolin described in described step (3).
10. the reuse method of a kind of waste and old methanol-to-olefin catalyst fine powder as claimed in claim 1, is characterized in that the mass content of solid in slurries described in described step is (3) 30 ~ 55%, grinding rear slurry ageing 6 ~ 36h.
The reuse method of 11. a kind of waste and old methanol-to-olefin catalyst fine powders as claimed in claim 10, is characterized in that described grinding rear slurry ageing 8 ~ 20h.
The reuse method of 12. a kind of waste and old methanol-to-olefin catalyst fine powders as claimed in claim 1, it is characterized in that spraying dry described in described step (3) adopts centrifugal spray drying device, sprayer inlet temperature is 350 ~ 550 DEG C, and outlet temperature is 110 ~ 190 DEG C.
13. methods as described in any one of claim 1-12, is characterized in that providing the molecular sieve catalyst that preceding method obtains.
The application of 14. molecular sieve catalysts as claimed in claim 13, is characterized in that molecular sieve catalyst is applied in methanol to olefins reaction.
CN201510456094.8A 2015-07-29 2015-07-29 Recycle method of catalyst fine powder obtained by preparation of olefin from waste and old methanol Pending CN105126903A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201510456094.8A CN105126903A (en) 2015-07-29 2015-07-29 Recycle method of catalyst fine powder obtained by preparation of olefin from waste and old methanol

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201510456094.8A CN105126903A (en) 2015-07-29 2015-07-29 Recycle method of catalyst fine powder obtained by preparation of olefin from waste and old methanol

Publications (1)

Publication Number Publication Date
CN105126903A true CN105126903A (en) 2015-12-09

Family

ID=54712672

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201510456094.8A Pending CN105126903A (en) 2015-07-29 2015-07-29 Recycle method of catalyst fine powder obtained by preparation of olefin from waste and old methanol

Country Status (1)

Country Link
CN (1) CN105126903A (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109772476A (en) * 2019-03-18 2019-05-21 新兴能源科技有限公司 A kind of DMTO device catalyst of deposed molecular sieve thin powder recovery method and application
CN114890435A (en) * 2022-06-22 2022-08-12 中国石油大学(华东) Hollow-structure SAPO-34 molecular sieve prepared by MTO waste catalyst and preparation method and application thereof
CN115069297A (en) * 2022-06-22 2022-09-20 中国石油大学(华东) Long-life SAPO-34 catalyst prepared by taking MTO waste catalyst as raw material, and preparation method and application thereof
CN115518682A (en) * 2021-06-25 2022-12-27 中国石油化工股份有限公司 Catalyst for preparing olefin from methanol, preparation method and application thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1140743B1 (en) * 1997-10-02 2005-10-05 CASALE ChEMICALS S.A. Catalytic process for the preparation of light olefins from methanol in a fluidised bed reactor
CN101555021A (en) * 2009-04-22 2009-10-14 神华集团有限责任公司 Method for preparing SAPO-34 molecular sieve by using crystallized residual liquid of SAPO-34 molecular sieve
CN102389834A (en) * 2011-08-30 2012-03-28 神华集团有限责任公司 Molecular sieve catalyst micro powder reutilization method as well as obtained product and application thereof
CN103172083A (en) * 2011-12-23 2013-06-26 正大能源材料(大连)有限公司 Comprehensive utilization method of silicon-aluminum-phosphorus molecular sieve synthesis liquid

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1140743B1 (en) * 1997-10-02 2005-10-05 CASALE ChEMICALS S.A. Catalytic process for the preparation of light olefins from methanol in a fluidised bed reactor
CN101555021A (en) * 2009-04-22 2009-10-14 神华集团有限责任公司 Method for preparing SAPO-34 molecular sieve by using crystallized residual liquid of SAPO-34 molecular sieve
CN102389834A (en) * 2011-08-30 2012-03-28 神华集团有限责任公司 Molecular sieve catalyst micro powder reutilization method as well as obtained product and application thereof
CN103172083A (en) * 2011-12-23 2013-06-26 正大能源材料(大连)有限公司 Comprehensive utilization method of silicon-aluminum-phosphorus molecular sieve synthesis liquid

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109772476A (en) * 2019-03-18 2019-05-21 新兴能源科技有限公司 A kind of DMTO device catalyst of deposed molecular sieve thin powder recovery method and application
CN115518682A (en) * 2021-06-25 2022-12-27 中国石油化工股份有限公司 Catalyst for preparing olefin from methanol, preparation method and application thereof
CN114890435A (en) * 2022-06-22 2022-08-12 中国石油大学(华东) Hollow-structure SAPO-34 molecular sieve prepared by MTO waste catalyst and preparation method and application thereof
CN115069297A (en) * 2022-06-22 2022-09-20 中国石油大学(华东) Long-life SAPO-34 catalyst prepared by taking MTO waste catalyst as raw material, and preparation method and application thereof
CN114890435B (en) * 2022-06-22 2023-08-25 中国石油大学(华东) Hollow-structure SAPO-34 molecular sieve prepared by MTO spent catalyst, and preparation method and application thereof
CN115069297B (en) * 2022-06-22 2023-09-12 中国石油大学(华东) Long-life SAPO-34 catalyst prepared by taking MTO spent catalyst as raw material, and preparation method and application thereof

Similar Documents

Publication Publication Date Title
CN105126902A (en) Quality improvement and recycle method of fine catalyst powder for methanol-based olefin preparation reaction
CN102389834B (en) Molecular sieve catalyst micro powder reutilization method as well as obtained product and application thereof
CN105126903A (en) Recycle method of catalyst fine powder obtained by preparation of olefin from waste and old methanol
AU2007283967B2 (en) A microsphere catalyst used for converting oxygen compound to olefine and preparation method thereof
CN1317244C (en) Method for producing propene using silicoaluminophosphate molecular sieve catalytic cracking
CN103561867B (en) Manufacture the improved method being used for that methanol is changed into the zeolite based catalysts of alkene
CN101134701A (en) Method for the decomposition of methyl tertiary-butyl ether
CN101121148A (en) Direct forming method of fluidized reaction catalyst containing molecular sieve
CN106890672B (en) A kind of methanol conversion light olefin catalyst processed and its preparation method and application
CN102923727A (en) Aluminosilicophosphate molecular sieve in multistage hole structure, and preparation method and application thereof
CN101318142B (en) Modification method for SAPO molecular sieve
CN105195213B (en) A kind of in-situ synthetic method of the catalyst of methanol/dimethyl ether conversion aromatic hydrocarbons
CN101612592A (en) A kind of preparation method of low abrasion microsphere catalyst produced in situ
CN107008255B (en) Nano diamond platinum catalyst and its preparation method and application for normal butane direct dehydrogenation butylene
CN1681753A (en) Process for preparing olefins from oxygenates
CN107774303A (en) Porous metals/molecular sieve composite catalyst, its preparation method and the purposes in preparing low-carbon olefin
CN101259425A (en) Method for preparing high abrasion resistance strength fluid bed catalyst
CN101259427A (en) Method for preparing high abrasion resistance strength molecular sieve fluid bed catalyst
CN100368356C (en) Method for producing propylene through catalytic cracking C4 olefin
CN105712832B (en) A method of isobutene is produced for raw material with MTO by-products carbon four
CN1192994C (en) Propylene producing process
CN103143388B (en) Preparation method of molecular sieve catalyst of olefin prepared from organic oxygen-containing compounds
CN104557397B (en) Method for producing propylene from n-butene
CN109701633A (en) Fluid catalyst, preparation method and its usage
CN110270369A (en) A kind of methanol, ethyl alcohol or dimethyl ether for microspherical catalyst used in low-carbon alkene preparation method and applications

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
TA01 Transfer of patent application right
TA01 Transfer of patent application right

Effective date of registration: 20170328

Address after: 518052 Guangdong city of Shenzhen province Qianhai Shenzhen Hong Kong cooperation zone before Bay Road No. 1 building 201 room A (located in Shenzhen Qianhai business secretary Co. Ltd.)

Applicant after: Shenzhen science and Technology Co., Ltd.

Address before: 030006 Shanxi, Taiyuan Xiaodian District Building No. 2, South Road, building 467

Applicant before: Taiyuan Dacheng Huanneng Chemical Technology Co., Ltd.

RJ01 Rejection of invention patent application after publication
RJ01 Rejection of invention patent application after publication

Application publication date: 20151209