CN115888803A - Preparation method and application of modified ZSM-35 molecular sieve catalyst - Google Patents
Preparation method and application of modified ZSM-35 molecular sieve catalyst Download PDFInfo
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- CN115888803A CN115888803A CN202211677478.9A CN202211677478A CN115888803A CN 115888803 A CN115888803 A CN 115888803A CN 202211677478 A CN202211677478 A CN 202211677478A CN 115888803 A CN115888803 A CN 115888803A
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 68
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 239000003054 catalyst Substances 0.000 title claims abstract description 66
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000002253 acid Substances 0.000 claims abstract description 23
- 238000001035 drying Methods 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 13
- 238000006317 isomerization reaction Methods 0.000 claims abstract description 8
- 238000010306 acid treatment Methods 0.000 claims abstract description 7
- 150000001336 alkenes Chemical class 0.000 claims abstract description 7
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 66
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 54
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 22
- 229910017604 nitric acid Inorganic materials 0.000 claims description 19
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 4
- 238000001125 extrusion Methods 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 abstract description 8
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 35
- 238000003756 stirring Methods 0.000 description 18
- 239000000203 mixture Substances 0.000 description 8
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 239000011230 binding agent Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 230000007935 neutral effect Effects 0.000 description 5
- 239000000126 substance Substances 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 241000219793 Trifolium Species 0.000 description 2
- 239000003929 acidic solution Substances 0.000 description 2
- 230000009849 deactivation Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000012847 fine chemical Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000006004 Quartz sand Substances 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 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
- 230000003321 amplification Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
Classifications
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- 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
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a preparation method and application of a modified ZSM-35 molecular sieve based catalyst, and belongs to the technical field of catalyst preparation. The preparation method comprises the steps of extruding, forming, drying and roasting the ZSM-35 molecular sieve, then placing the ZSM-35 molecular sieve in an acid solution for acid treatment, and finally drying and roasting the ZSM-35 molecular sieve again to obtain the modified ZSM-35 molecular sieve catalyst. The method has the characteristics of simple preparation process and low cost, and the modified ZSM-35 molecular sieve catalyst is applied to n-butene isomerization reaction, has better olefin conversion rate, selectivity and yield than the catalytic effect of a commercial industrial ZSM-35 molecular sieve under the same reaction condition, and can be applied to industrial large-scale production.
Description
Technical Field
The invention relates to the technical field of catalyst preparation, in particular to a preparation method of a modified ZSM-35 molecular sieve and application thereof in olefin isomerization reaction.
Background
With the development of high value-added fine chemical products becoming faster and faster, the demand of fine chemical raw materials such as isoolefins and the like is also increasing rapidly. The development of olefin skeleton isomerization industrial process provides a feasible way for increasing the yield of the isoolefin, and has great economic benefit and social benefit. Currently, ZSM-35 has been proven as an optimal catalyst for skeletal isomerization of n-butene, and has been industrially used.
The catalyst powder is inconvenient in practical application due to the fact that the particle size of the catalyst powder is too small, and has the defects of difficult recovery, easy deactivation, easy aggregation and the like, so that the catalyst powder needs to be molded in advance. The binder is generally added during the shaping process, and is generally present in an amount of from 10 to 40% by weight, or even more, based on the total weight of the catalyst, in order to give the catalyst a particular shape and a certain mechanical strength, which is necessary in this regard. The existing industrial ZSM-35 molecular sieve catalyst contains a large amount of binder, however, the binder is generally an inert component, and the addition of the binder also has a dilution effect on the active center of the molecular sieve substantially, so that the actual reaction space velocity is increased, and the deactivation of the catalyst is accelerated. In addition, the binder has a certain pore blocking effect on the molecular sieve, which affects the diffusion performance and finally causes poor stability of the catalyst. The invention adopts an acid treatment mode to treat the formed ZSM-35 molecular sieve so as to remove aluminum on the outer surface of the molecular sieve and remove amorphous substances in the pore channels of the molecular sieve, thereby obtaining the formed catalyst with high isomerization activity and good stability.
Disclosure of Invention
The technical problem to be solved by the invention is to overcome the defects of the existing catalyst extrusion molding method, and provide the acid-treated and molded ZSM-35 molecular sieve and the application thereof.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a preparation method of a modified ZSM-35 molecular sieve catalyst comprises the following steps of extruding, forming, drying and roasting the ZSM-35 molecular sieve catalyst, then placing the ZSM-35 molecular sieve catalyst in an acid solution for acid treatment, and finally drying and roasting the ZSM-35 molecular sieve catalyst again to obtain the modified ZSM-35 molecular sieve catalyst;
the molar ratio of silicon oxide to aluminum oxide in the ZSM-35 molecular sieve catalyst is 5-15; the diameter of the ZSM-35 molecular sieve catalyst is 1.5-5.0mm by extrusion molding; the cross section of the material is round, and can also be at least one of strip, clover, cylinder middle hole, clover, dumbbell, honeycomb, wheel or cross-hole cylinder.
Preferably, the drying temperature is 80-120 ℃, and the drying time is 6-12 hours.
Preferably, the roasting temperature is 450-650 ℃, and the roasting time is 3-6 hours.
Preferably, the acidic solution is at least one of a nitric acid solution, a citric acid solution or an acetic acid solution.
More preferably, the mass concentration of the nitric acid solution is 0.2-10 wt%; the concentration of the citric acid solution is 2-20 wt%, and the mass concentration of the acetic acid solution is 2-20 wt%.
More preferably, the acidic solution is prepared by mixing a nitric acid solution and a citric acid solution according to a mass ratio of 0.2-5:2-10 by mixing, or
The acid solution is prepared from citric acid solution and acetic acid solution according to the mass ratio of 2-10:2-10 of the above-mentioned raw materials or,
the acid solution is formed by mixing a nitric acid solution and an acetic acid solution according to the mass ratio of 0.2-5.
Preferably, the temperature of the acid treatment is 25-120 ℃, and the treatment time is 1-24h.
The invention also provides a modified ZSM-35 molecular sieve catalyst prepared by the method.
The invention also provides application of the modified ZSM-35 molecular sieve catalyst, wherein the catalyst is applied to olefin isomerization reaction at the reaction temperature of 250-350 ℃ and airThe speed is 1-7h -1 。
The invention has the beneficial effects that:
the invention provides a preparation method of a modified ZSM-35 molecular sieve catalyst, the catalyst prepared by the method has high olefin conversion rate and selectivity, the conversion rate of butylene is more than 44% and can reach 54.3% at most when the catalyst is used for olefin isomerization reaction, the selectivity of isobutene product can reach 93.1% at most, the reaction performance reaches the effect of an unformed powdery molecular sieve, and the catalyst has high mechanical strength and good application value.
Detailed Description
The present invention will be further described with reference to the following examples.
In the embodiment of the invention, the ZSM-35 molecular sieve adopted has the mole ratio of silica to alumina of 1:10.5.
example 1
A preparation method of a modified ZSM-35 molecular sieve catalyst comprises the following steps:
weighing 28g of nitric acid (67%), adding the nitric acid into 722g of deionized water, and uniformly stirring to prepare a nitric acid solution;
extruding 80g of ZSM-35 molecular sieve catalyst into strips with the diameter of 3.0mm, drying at 120 ℃ for 10h, roasting at 550 ℃ for 4h, then placing in a nitric acid solution, slightly stirring, heating to 60 ℃, and keeping slightly stirring for 3h; filtering, washing to neutrality, transferring to an oven for drying at 120 ℃ for 10h, and finally roasting in a muffle furnace at 500 ℃ for 4h to obtain the nitric acid modified ZSM-35 molecular sieve catalyst.
Example 2
A preparation method of a modified ZSM-35 molecular sieve catalyst comprises the following steps:
weighing 58g of citric acid, adding the citric acid into 692g of deionized water (7.7 percent), and uniformly stirring to prepare a citric acid solution;
extruding 80g of ZSM-35 molecular sieve catalyst into a strip shape with the diameter of 3.0mm, drying at 120 ℃ for 10h, roasting at 550 ℃ for 4h, then placing in a citric acid solution for slight stirring, heating to 90 ℃, and keeping the slight stirring for 12h; filtering and washing to be neutral; transferring the mixture to an oven for drying at 120 ℃ for 10h, and finally roasting the mixture in a muffle furnace for 4h at 500 ℃ to obtain the citric acid modified ZSM-35 molecular sieve catalyst.
Example 3
A preparation method of a modified ZSM-35 molecular sieve catalyst comprises the following steps:
weighing 54g of acetic acid, adding into 696g of deionized water, and stirring uniformly to prepare an acetic acid solution;
extruding 80g of ZSM-35 molecular sieve catalyst into a strip with the diameter of 3.0mm, drying at 120 ℃ for 10h, roasting at 550 ℃ for 4h, then placing in an acetic acid solution for slight stirring, heating to 90 ℃, and keeping slightly stirring for 12h; filtering and washing to be neutral; transferring the solution to an oven for drying at 120 ℃ for 10h, and finally roasting the solution in a muffle furnace for 4h at 500 ℃ to obtain the acetic acid modified ZSM-35 molecular sieve catalyst.
Example 4
A preparation method of a modified ZSM-35 molecular sieve catalyst comprises the following steps:
weighing 28g of nitric acid (67%) and 58g of citric acid in sequence, adding the nitric acid and the citric acid into 664g of deionized water, and uniformly stirring to prepare a mixed acid solution of the nitric acid and the citric acid;
extruding 80g of ZSM-35 molecular sieve catalyst into strips with the diameter of 3.0mm, drying at 120 ℃ for 10h, roasting at 550 ℃ for 4h, then placing in a mixed acid solution for slight stirring, heating to 60 ℃, and keeping the slight stirring for 3h; filtering and washing to be neutral; transferring the mixture to an oven for drying at 120 ℃ for 10h, and finally roasting the mixture in a muffle furnace for 4h at 500 ℃ to obtain the nitric acid and citric acid mixed acid modified ZSM-35 molecular sieve catalyst.
Example 5
A preparation method of a modified ZSM-35 molecular sieve catalyst comprises the following steps:
weighing 28g of nitric acid (67%), 54g of acetic acid and 668g of deionized water, and uniformly stirring to prepare a nitric acid and acetic acid mixed acid solution;
extruding 80g of ZSM-35 molecular sieve catalyst into strips with the diameter of 3.0mm, drying at 120 ℃ for 10h, roasting at 550 ℃ for 4h, then placing in a mixed acid solution for slight stirring, heating to 60 ℃, and keeping the slight stirring for 3h; filtering and washing to be neutral; transferring the mixture to an oven for drying at 120 ℃ for 10h, and finally roasting in a muffle furnace at 500 ℃ for 4h to obtain the nitric acid and acetic acid mixed acid modified ZSM-35 molecular sieve catalyst.
Example 6
A preparation method of a modified ZSM-35 molecular sieve catalyst comprises the following steps:
weighing 58g of citric acid and 54g of acetic acid, adding into 638g of deionized water, and uniformly stirring to prepare a mixed acid solution of citric acid and acetic acid;
extruding 80g of ZSM-35 molecular sieve catalyst into strips with the diameter of 3.0mm, drying at 120 ℃ for 10h, roasting at 550 ℃ for 4h, then placing in a mixed acid solution for slight stirring, heating to 120 ℃, and keeping the slight stirring for 12h; filtering and washing to be neutral; transferring the mixture to an oven for drying at 120 ℃ for 10h, and finally roasting the mixture in a muffle furnace for 4h at 500 ℃ to obtain the citric acid and acetic acid mixed acid modified ZSM-35 molecular sieve catalyst.
Examples 7 to 14
The composition of the acid solution is a nitric acid and citric acid two-substance combined solution, the mass concentration of each species of the solution is shown in table 1, and other treatment conditions are the same as those of example 4.
TABLE 1
Example 15
The activity of the ZSM-35 molecular sieve catalysts prepared in examples 1 to 14 was evaluated, while using an industrial ZSM-35 molecular sieve commercially available from Mitsubishi GmbH as a control.
The evaluation method comprises the following steps: the catalyst activity test is carried out on a fixed bed reactor, and the reaction pressure is 0.1MPa. The experimental procedure was as follows: 4g of catalyst (20-40 meshes) and 4g of quartz sand (20-40 meshes) are weighed, mixed uniformly and then put into a stainless steel reaction tube with the diameter of 10 mm. Before reaction, the catalyst is heated to the reaction temperature under the nitrogen flow, the lh is activated at the temperature, then 1-butene raw material gas is introduced for reaction, the reaction enters a chromatographic analysis system for on-line analysis after sampling through a six-way valve every 4 hours, and liquid products are analyzed under the line. Trans formThe conditions are as follows: reaction conditions are as follows: t =290 ℃, P =0.1MPa and airspeed of 4h -1 The results are shown in Table 2:
TABLE 2
As can be seen from table 1: compared with the catalyst prepared by the modification of a single-substance acid solution on the market, the modified ZSM-35 molecular sieve prepared by the acid solution with the combination of two substances has the highest 1-butene conversion rate and isobutene selectivity, wherein the conversion rate and isobutene selectivity of the molecular sieve 1-butene are highest when the molecular sieve is treated by the mixed acid solution which is composed of 0.8 percent of nitric acid concentration and 2 percent of citric acid concentration in example 11. The method for forming the molecular sieve by acid treatment has obvious advantages, basically maintains the mechanical strength of the finished product, improves the catalytic performance, and can be used for industrial amplification production.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and amendments can be made without departing from the principle of the present invention, and these modifications and amendments should also be considered as the protection scope of the present invention.
Claims (9)
1. A preparation method of a modified ZSM-35 molecular sieve catalyst is characterized by comprising the following steps: the method comprises the following steps of extruding, forming, drying and roasting the ZSM-35 molecular sieve, then placing the ZSM-35 molecular sieve in an acid solution for acid treatment, and finally drying and roasting the ZSM-35 molecular sieve again to obtain a modified ZSM-35 molecular sieve catalyst;
the mol ratio of silicon oxide to aluminum oxide in the ZSM-35 molecular sieve is 5-15; and the diameter of the ZSM-35 molecular sieve is 1.5-5.0mm by extrusion molding.
2. The method of preparing a modified ZSM-35 molecular sieve catalyst as claimed in claim 1, wherein: the drying temperature is 80-120 ℃, and the drying time is 6-12 hours.
3. The method of preparing a modified ZSM-35 molecular sieve catalyst as claimed in claim 1, wherein: the roasting temperature is 450-650 ℃, and the roasting time is 3-6 hours.
4. The method of preparing a modified ZSM-35 molecular sieve catalyst as claimed in claim 1, wherein: the acid solution is at least one of a nitric acid solution, a citric acid solution or an acetic acid solution.
5. The method of preparing a modified ZSM-35 molecular sieve catalyst as claimed in claim 4, wherein: the mass concentration of the nitric acid solution is 0.2-10 wt%; the concentration of the citric acid solution is 2-20 wt%, and the mass concentration of the acetic acid solution is 2-20 wt%.
6. The method of preparing a modified ZSM-35 molecular sieve catalyst as claimed in claim 5, wherein: the acid solution is prepared by mixing a nitric acid solution and a citric acid solution according to the mass ratio of 0.2-5:2-10 are mixed, or
The acid solution is prepared from citric acid solution and acetic acid solution according to the mass ratio of 2-10:2-10 of the above-mentioned raw materials or,
the acid solution is formed by mixing a nitric acid solution and an acetic acid solution according to the mass ratio of 0.2-5.
7. The method of preparing a modified ZSM-35 molecular sieve catalyst as claimed in claim 1, wherein: the temperature of the acid treatment is 25-120 ℃, and the treatment time is 1-24h.
8. A modified ZSM-35 molecular sieve catalyst, prepared according to the method of any of claims 1 to 7.
9. A kind ofThe use of the modified ZSM-35 molecular sieve catalyst of claim 8, wherein the catalyst is used in an olefin isomerisation reaction at a reaction temperature of 250-350 ℃ and a space velocity of 1-7h - 1。
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0641299A1 (en) * | 1992-05-11 | 1995-03-08 | Mobil Oil Corp | N-olefin skeletal isomerization process. |
| US5449851A (en) * | 1991-09-16 | 1995-09-12 | Mobil Oil Corporation | Highly selective n-olefin isomerization process using ZSM-35 |
| CN1511637A (en) * | 2002-12-29 | 2004-07-14 | 中国石油化工股份有限公司齐鲁分公司 | Normal olefin skeleton isomerization catalyst and its preparing method |
| CN102603452A (en) * | 2012-02-07 | 2012-07-25 | 王伟跃 | Method for preparing isoalkenes through isomerizing linear alkenes |
| CN103934039A (en) * | 2013-01-23 | 2014-07-23 | 中国石油化工股份有限公司 | Method of enhancing strength of molecular sieve catalyst |
| CN113122313A (en) * | 2020-01-15 | 2021-07-16 | 中国石油天然气股份有限公司 | Olefin isomerization method |
| CN114713278A (en) * | 2022-03-30 | 2022-07-08 | 中触媒新材料股份有限公司 | Preparation method of full-crystalline ZSM-35 molecular sieve and application thereof in olefin isomerization reaction |
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-
2022
- 2022-12-26 CN CN202211677478.9A patent/CN115888803A/en active Pending
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| Title |
|---|
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