CN111013639A - Butene double bond isomerization catalyst and application thereof - Google Patents

Butene double bond isomerization catalyst and application thereof Download PDF

Info

Publication number
CN111013639A
CN111013639A CN201811175352.5A CN201811175352A CN111013639A CN 111013639 A CN111013639 A CN 111013639A CN 201811175352 A CN201811175352 A CN 201811175352A CN 111013639 A CN111013639 A CN 111013639A
Authority
CN
China
Prior art keywords
zsm
butene
molecular sieve
double bond
bond isomerization
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
CN201811175352.5A
Other languages
Chinese (zh)
Inventor
龚海燕
刘俊涛
张旭
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.)
China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
Original Assignee
China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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 China Petroleum and Chemical Corp, Sinopec Shanghai Research Institute of Petrochemical Technology filed Critical China Petroleum and Chemical Corp
Priority to CN201811175352.5A priority Critical patent/CN111013639A/en
Publication of CN111013639A publication Critical patent/CN111013639A/en
Pending legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/80—Mixtures of different zeolites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B01J29/405—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/65—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the ferrierite type, e.g. types ZSM-21, ZSM-35 or ZSM-38, as exemplified by patent documents US4046859, US4016245 and US4046859, respectively
    • B01J29/655—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the ferrierite type, e.g. types ZSM-21, ZSM-35 or ZSM-38, as exemplified by patent documents US4046859, US4016245 and US4046859, respectively containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/7049—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/22—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by isomerisation
    • C07C5/23—Rearrangement of carbon-to-carbon unsaturated bonds
    • C07C5/25—Migration of carbon-to-carbon double bonds
    • C07C5/2506—Catalytic processes
    • C07C5/2518—Catalytic processes with crystalline alumino-silicates, e.g. molecular sieves
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • B01J2229/183—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself in framework positions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/30—After treatment, characterised by the means used
    • B01J2229/42—Addition of matrix or binder particles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
    • C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • C07C2529/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
    • C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • C07C2529/65—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the ferrierite type, e.g. types ZSM-21, ZSM-35 or ZSM-38
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
    • C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • C07C2529/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups C07C2529/08 - C07C2529/65
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
    • C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • C07C2529/80—Mixtures of different zeolites

Abstract

The invention relates to a butene double bond isomerization catalyst and application thereof. The catalyst comprises 30-90 parts by weight of Zr-ZSM molecular sieve and 10-70 parts by weight of binder, wherein the weight part of the Zr-ZSM molecular sieve is relative to the total weight part of the binder; wherein Zr is present in the molecular sieve framework.

Description

Butene double bond isomerization catalyst and application thereof
Technical Field
The invention relates to a butene double bond isomerization catalyst and application thereof.
Background
1-butene is α -olefin with relatively active chemical property, is mainly used for producing Linear Low Density Polyethylene (LLDPE), High Density Polyethylene (HDPE), Polybutylene (PB) resin, decanol and the like, and has wide application, in recent years, the global demand for polyethylene is rapidly increased, so the demand for 1-butene serving as a comonomer is increased, however, most of domestic 1-butene manufacturers are self-used and rarely sell the 1-butene to other parts, so the purchase of the 1-butene is relatively difficult, and particularly, enterprises with relatively large gaps for the 1-butene exist.
Currently, there are two main routes for global 1-butene production, one is oligomerization process using ethylene as raw material, and the other is refinery C4C, cracking4Or coal-to-olefin byproduct mixed C4Is obtained by separating raw materials. The latter is commonly adopted in China for the mixed C4Butadiene extraction and hydrogenation are carried out, isobutene is removed through etherification, and then 1-butene products are obtained through rectification separation. But the yield of 1-butene in this route is limited by the source of 1-butene in the feed. Most petrochemical companies in the world use residual C rich in 2-butene4Hydrocarbons are used as fuels. If the part of 2-butene is converted into 1-butene through isomerization reaction, a new path for producing the 1-butene can be opened up.
In recent years, a great deal of research and development has been carried out on the process for producing 1-butene by isomerizing 2-butene by related petrochemical companies at home and abroad. For example, CN102267853A discloses a method for producing 1-butene by isomerizing 2-butene, which adopts a surface area of 150-210 m2Taking alumina per gram as a carrier, dissolving 0.146-23.82 parts by weight of metal salt in 82-100 parts by weight of deionized water to prepare an aqueous solution, and then soaking 57 parts by weight of catalyst carrier; standing and soaking for 16-24 hours at room temperature, filtering out residual liquid, drying for 4-10 hours at the temperature of 120-160 ℃ until water is completely removed, and roasting for 1-12 hours at the temperature of 500-600 ℃ to obtain a metal composite oxide catalyst; the catalyst prepared by the method is filled in a fixed bed catalytic reactor, 2-butylene gas with the content of 85.0-99.0% passes through a catalyst bed layer, the temperature is 300-480 ℃, the pressure is 0.1-0.5 Mpa, and the gas hourly space velocity of the feed of the 2-butylene is 60-900 hours-1Carrying out double-bond isomerization reaction under the condition of (1), and carrying out timing sampling analysis on gas after the reaction to obtain the 1-butene with the content of 19.0-27.0%. The catalyst prepared by the method has low activity and selectivity, and needs high reaction temperature; meanwhile, the isobutene content in the reaction product is higher.
Disclosure of Invention
The present inventors have assiduously studied on the basis of the prior art and have accomplished the present invention by solving at least one of the aforementioned problems by using a molecular sieve containing framework zirconium as an active component of a catalyst.
In particular, the invention relates to a butene double bond isomerization catalyst. The butene double bond isomerization catalyst comprises 30-90 parts by weight of Zr-ZSM molecular sieve and 10-70 parts by weight of binder, wherein the weight part of the Zr-ZSM molecular sieve is relative to the total weight part of the binder; wherein Zr is present in the molecular sieve framework.
According to one aspect of the invention, the Zr-ZSM molecule screens one of the group consisting of Zr-ZSM-5, Zr-ZSM-11, Zr-ZSM-35 and Zr-ZSM-39.
According to one aspect of the invention, the Zr-ZSM molecule screens a mechanical mixture of at least two of the group consisting of Zr-ZSM-5, Zr-ZSM-11, Zr-ZSM-35 and Zr-ZSM-39.
According to one aspect of the invention, the Zr-ZSM molecule screens eutectic molecular sieves of at least two of the group consisting of Zr-ZSM-5, Zr-ZSM-11, Zr-ZSM-35 and Zr-ZSM-39, preferably Zr-ZSM-5/ZSM-11 eutectic molecular sieves.
According to an aspect of the present invention, the binder is at least one selected from the group consisting of alumina and silica.
According to one aspect of the invention, the catalyst comprises 40 to 80 parts of the Zr-ZSM molecular sieve and 20 to 60 parts of the binder, relative to the total weight parts of the Zr-ZSM molecular sieve and the binder; preferably, the Zr-ZSM molecular sieve comprises 50-80 parts of Zr-ZSM molecular sieve and 20-50 parts of binder.
According to one aspect of the invention, in the Zr-ZSM molecular sieve, the molar ratio of silicon to zirconium is 50-1000, preferably 100-500.
According to one aspect of the invention, the catalyst does not contain an alkaline earth metal element or an oxide thereof.
According to an aspect of the present invention, the alkaline earth metal element is at least one selected from the group consisting of magnesium, calcium, strontium, and barium; in particular magnesium.
The invention also relates to a butene double bond isomerization catalyst. The catalyst consists of 30-90 parts by weight of Zr-ZSM-5/ZSM-11 eutectic molecular sieve and 10-70 parts by weight of binder; wherein, the molar ratio of silicon to zirconium is 50-1000, preferably 100-500; zr exists in the eutectic molecular sieve framework.
The invention also relates to a butene double bond isomerization method. The method comprises the step of contacting a stream containing 2-butene with the butene double bond isomerization catalyst to obtain 1-butene.
According to one aspect of the invention, the contact temperature is 150-280 ℃, the pressure is 0-1 MPa, and the weight space velocity is 1-10 hours-1(ii) a The preferable contact temperature is 180-270 ℃, the pressure is 0.5-1 MPa, and the weight space velocity is 2-5 hours-1。
According to one aspect of the invention, the stream containing 2-butene is derived from a refinery catalytic cracking unit, an ethylene plant steam cracking unit or a coal-to-olefin unit byproduct mixed C-IV stream, preferably a C-IV stream obtained by removing 1, 3-butadiene and isobutene from the refinery catalytic cracking unit, the ethylene plant steam cracking unit or the coal-to-olefin unit byproduct mixed C-IV stream.
According to one aspect of the invention, said 2-butene-containing stream is a mixture comprising 1-butene and 2-butene which does not meet thermodynamic equilibrium values.
According to one aspect of the invention, the 2-butene-containing stream has a mass concentration of 1-butene of less than 4% and a mass concentration of 2-butene of greater than 45%.
According to one aspect of the invention, the mass concentration of 1, 3-butadiene in the 2-butene-containing stream is less than 30 ppm.
The invention has the beneficial effects that:
according to the invention, the reaction temperature is low, the reaction condition is mild, and the energy is saved.
According to the invention, the conversion rate of 2-butene is high and is close to the thermodynamic equilibrium conversion rate at the temperature; and under the premise of high conversion rate, the selectivity of 1-butene is high. For example, at a reaction temperature of 250 ℃, a reaction pressure of 0.4MPa and a weight space velocity of 5 hours-1Under the condition, the conversion rate of 2-butene is more than 16.8 wt%, the thermodynamic equilibrium conversion rate is 16.9 wt% at the temperature, and the selectivity of 1-butene can reach 99.84%.
The invention is further described below by means of specific embodiments.
Detailed Description
The following describes in detail specific embodiments of the present invention. It is to be noted, however, that the scope of the present invention is not limited thereto, but is defined by the appended claims.
All publications, patent applications, patents, and other references mentioned in this specification are herein incorporated by reference in their entirety. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. In case of conflict, the present specification, including definitions, will control.
When the specification concludes with claims with the heading "known to those skilled in the art", "prior art", or the like, to derive materials, substances, methods, procedures, devices, or components, etc., it is intended that the subject matter derived from the heading encompass those conventionally used in the art at the time of filing this application, but also include those that are not currently in use, but would become known in the art to be suitable for a similar purpose.
In the context of the present specification, anything or things which are not mentioned, except where explicitly stated, are directly applicable to those known in the art without any changes. Moreover, any embodiment described herein may be freely combined with one or more other embodiments described herein, and the technical solutions or concepts resulting therefrom are considered part of the original disclosure or original disclosure of the invention, and should not be considered as new matters not disclosed or contemplated herein, unless a person skilled in the art would consider such a combination to be clearly unreasonable.
Unless otherwise expressly indicated, all percentages, parts, ratios, etc. mentioned in this specification are by weight unless otherwise not in accordance with the conventional knowledge of those skilled in the art.
Where not explicitly stated, reference to pressure within this specification is to gauge pressure.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein. In the following, various technical solutions can in principle be combined with each other to obtain new technical solutions, which should also be regarded as specifically disclosed herein.
It should be noted that the 2-butene double bond isomerization reaction to produce 1-butene is typically a reversible reaction, and generally the distribution of butene isomerization products is mainly controlled by thermodynamic factors. Therefore, different thermodynamic equilibrium conversions will be associated at different temperatures. Thermodynamic equilibrium conversion can be thermodynamically calculated for the reaction process by means of the Gibbs free energy minimum principle, which is well known to those skilled in the art.
The invention relates to a butene double bond isomerization catalyst. The butene double bond isomerization catalyst comprises 30-90 parts by weight of Zr-ZSM molecular sieve and 10-70 parts by weight of binder, wherein the weight part of the Zr-ZSM molecular sieve is relative to the total weight part of the binder; wherein Zr is present in the Zr-ZSM molecular sieve framework.
It is well known to those skilled in the art that the acidic strength of a molecular sieve is very important for the catalytic reaction of the molecular sieve as the active component of the catalyst. For butene isomerization reaction, if the catalyst acidity is too strong, 2-butene can be efficiently isomerized into 1-butene, but a large amount of side reactions such as skeletal isomerization, dehydrogenation, cracking and the like can occur at the same time, so that the selectivity of the reaction is reduced; conversely, if the catalyst is less acidic, this results in poor catalyst activity and low 2-butene conversion. In addition, the butene double bond isomerization reaction is an equilibrium reaction, and the conversion rate and the reaction temperature have a great relationship. The reaction temperature is high, the catalyst activity is high, the 2-butene conversion rate is high, but the side reaction is increased. Therefore, adjusting the acid strength of the catalyst within the appropriate range is critical to ensure that the conversion and selectivity are within the most economical range. According to the invention, the ZSM molecular sieve with the zirconium-containing framework is used as the active component of the catalyst, and the acidity of the catalyst is properly improved, so that the previous task can be ensured to be completed at a lower reaction temperature.
According to the invention, in the Zr-ZSM molecular sieve, the molar ratio of silicon to aluminum is 50-500, preferably 100-450, and more preferably 200-400; the molar ratio of silicon to zirconium is 50 to 1000, preferably 100 to 500.
According to the present invention, the Zr-ZSM molecular sieve may be one selected from the group consisting of Zr-ZSM-5, Zr-ZSM-11, Zr-ZSM-35 and Zr-ZSM-39; or a mechanical mixture of at least two selected from the group consisting of Zr-ZSM-5, Zr-ZSM-11, Zr-ZSM-35 and Zr-ZSM-39; it may also be an eutectic molecular sieve of at least two selected from the group consisting of Zr-ZSM-5, Zr-ZSM-11, Zr-ZSM-35 and Zr-ZSM-39, preferably Zr-ZSM-5/ZSM-11 eutectic molecular sieve. The eutectic molecular sieves described herein, which may also be referred to in the art as intergrown molecular sieves, are distinguished from simple mechanical mixtures by having two or more distinct phases of intergrown materials of crystalline structure in one molecular sieve composition.
According to the present invention, the binder is at least one selected from the group consisting of alumina and silica.
According to an embodiment of the present invention, the catalyst does not contain an alkaline earth metal element or an oxide thereof from the viewpoint of more favorable isomerization reaction. The alkaline earth metal element is at least one selected from the group consisting of magnesium, calcium, strontium, and barium; in particular magnesium.
According to one embodiment of the invention, the butene double bond isomerization catalyst consists of 30-90 parts by weight of Zr-ZSM-5/ZSM-11 eutectic molecular sieve and 10-70 parts by weight of binder; wherein, the molar ratio of silicon to zirconium is 50-1000, preferably 100-500; zr exists in the eutectic molecular sieve framework.
The invention also relates to an isomerization method. The method comprises the step of contacting a stream containing 2-butene with the butene double bond isomerization catalyst to obtain 1-butene.
According to the invention, the contact temperature is 150-280 ℃, the pressure is 0-1 MPa, and the weight space velocity is 1-10 hours-1(ii) a The preferable contact temperature is 180-270 ℃, the pressure is 0.5-1 MPa, and the weight space velocity is 2-5 hours-1。
According to the invention, the stream containing 2-butene is derived from a refinery catalytic cracking unit, an ethylene plant steam cracking unit or a coal-to-olefin unit byproduct mixed C-IV stream, and preferably is derived from a refinery catalytic cracking unit, an ethylene plant steam cracking unit or a coal-to-olefin unit byproduct mixed C-IV stream from which 1, 3-butadiene and isobutene are removed.
According to the invention, said stream comprising 2-butene is a mixture comprising 1-butene and 2-butene which does not comply with thermodynamic equilibrium values.
According to the invention, the 2-butene-containing stream has a mass concentration of 1-butene lower than 4% and a mass concentration of 2-butene higher than 45%.
According to the invention, the mass concentration of 1, 3-butadiene in the stream containing 2-butene is preferably less than 30 ppm. Too much 1, 3-butadiene in the feed will produce a large amount of polymer, which affects not only the product quality but also the stability of the catalyst.
The catalyst described in the present invention can be prepared by the following method. The method comprises the following steps: crystallizing a mixture (hereinafter, collectively referred to as a mixture) comprising a template, a zirconium source, a silicon source, an aluminum source, and water to obtain a Zr-ZSM molecular sieve, and a step of molding the Zr-ZSM molecular sieve with a binder.
Wherein the template is at least one selected from the group consisting of tetrapropylammonium hydroxide, tetrapropylammonium bromide, n-butylamine, tetramethylethylenediamine, cyclohexylamine, n-propylamine, and hexamethyltetramine.
The zirconium source, any zirconium source conventionally used in the art for this purpose may be used, including but not limited to zirconium nitrate, zirconium oxychloride, and zirconium isopropoxide, with zirconium nitrate and zirconium oxychloride being preferred.
As the silicon source, any silicon source conventionally used in the art for this purpose can be used. Examples thereof include sodium silicate, silica sol and silicate ester. These silicon sources may be used singly or in combination in a desired ratio.
As the aluminum source, any aluminum source conventionally used in the art for this purpose can be used. Examples thereof include aluminum sol and aluminum hydroxide. These aluminum sources may be used singly or in combination in a desired ratio.
In the mixture, the template agent and the zirconium source (as ZrO)2Calculated), the silicon source (in SiO)2Calculated as Al), an aluminum source (calculated as Al)2O3Calculated) and water in a molar ratio of: 0.1-0.5: 0.001-0.025: 1: 0-0.08: 35-170; preferably: 0.2-0.4: 0.005-0.025: 0.005-0.06: 35-170. Preferably, the mixture is controlled to have a pH of 4 to 9, and any acid or base conventionally used in the art for this purpose may be used therefor, such as hydrochloric acid, nitric acid, sulfuric acid, NaOH, KOH, and aqueous ammonia may be cited.
The crystallization may be performed in any manner conventionally known in the art, for example, a method of subjecting the mixture to hydrothermal crystallization under crystallization conditions may be exemplified. Crystallization may be in the presence of stirring as desired. The crystallization conditions include: the temperature is 120-200 ℃, and the time is 20-80 hours.
Preferably, an ageing step is included, carried out before crystallization, the ageing conditions including: the aging temperature is 30-75 ℃, and the aging time is 10-48 hours.
After the crystallization is completed, the Zr-ZSM molecular sieve may be separated from the obtained reaction mixture by any separation means conventionally known. The separation method includes, for example, a method of filtering, washing and drying the obtained product mixture. Here, the filtering, washing and drying may be performed in any manner conventionally known in the art. As a specific example, as the filtration, for example, the obtained product mixture may be simply filtered with suction. Examples of the washing include washing with deionized water and/or ethanol. The drying temperature is, for example, 40 to 250 ℃, preferably 60 to 150 ℃, and the drying time is, for example, 8 to 30 hours, preferably 10 to 20 hours. The drying may be carried out under normal pressure or under reduced pressure.
According to the requirement, the Zr-ZSM molecular sieve obtained by crystallization can be roasted to remove the organic template agent, the water and the like possibly existing, thereby obtaining the roasted molecular sieve. The calcination can be carried out in any manner conventionally known in the art, for example, the calcination temperature is generally 300 to 800 ℃, preferably 400 to 650 ℃, and the calcination time is generally 1 to 10 hours, preferably 3 to 6 hours. In addition, the calcination is generally carried out in an oxygen-containing atmosphere, such as air or oxygen.
And mixing the Zr-ZSM molecular sieve with a binder, and molding to obtain the catalyst. The catalyst may be in the form of any molded article (e.g., a bar, a clover, etc.), and may be obtained in any manner conventionally known in the art, without particular limitation. As the binder, any binder conventionally used in the art for this purpose can be used. For example, alumina or silica can be cited. Preferably, a pore-forming agent may be added during molding. As the porogen, any porogen conventionally used in the art for this purpose can be used. Examples thereof include sesbania powder and methyl cellulose.
The molded catalyst may be dried and calcined as necessary. The drying may be carried out in any manner conventionally known in the art, and the drying temperature may be, for example, 40 to 250 ℃, preferably 60 to 150 ℃, and the drying time may be, for example, 8 to 30 hours, preferably 10 to 20 hours. The drying may be carried out under normal pressure or under reduced pressure. The calcination can be carried out in any manner conventionally known in the art, for example, the calcination temperature is generally 300 to 800 ℃, preferably 400 to 650 ℃, and the calcination time is generally 1 to 10 hours, preferably 3 to 6 hours. In addition, the calcination is generally carried out in an oxygen-containing atmosphere, such as air or oxygen.
In the preparation method of the catalyst, the mixture does not contain an alkaline earth metal source from the viewpoint of more favorable isomerization reaction. The alkaline earth metal is at least one selected from the group consisting of magnesium, calcium, strontium, and barium; in particular magnesium. The phrase "not including an alkaline earth metal source" as used herein means that the alkaline earth metal source is not intentionally or actively introduced during the production process.
In the present invention, the composition of the catalyst was analyzed by ICP (inductively coupled plasma) and XRF (X-ray fluorescence) methods. ICP was used to test the zirconium content of the catalyst under the following test conditions: an iCAP7600Duo inductively coupled plasma emission spectrometer of American Sammer Feishell company is adopted, zirconium oxide is used as a standard sample, and the RF power of the instrument is 1.2 KW; the carrier gas flow is 0.72L/min; the flow rate of the cooling gas is 15L/min; the pump flow rate was 1.0ml/min and the analytical wavelength was 335 nm. XRF was used to test the content of molecular sieve in the catalyst under the following test conditions: a Rigaku ZSX 100e type XRF instrument is adopted, a rhodium target is used as an excitation source, the maximum power is 3600W, the tube voltage is 60KV, and the tube current is 120 mA.
The crystal phase of the catalyst is performed on a Bruker D8 polycrystalline X-ray diffraction (XRD) instrument, a graphite monochromator is used, a Cu-Ka ray source is used (the K α 1 wavelength lambda is 0.15406nm), the scanning angle 2 theta is 5-50 degrees, and the scanning speed is 1/min.
The existence form of Zr in the catalyst is determined by adopting a Cary5000 type ultraviolet-visible spectrum (UV-vis) instrument, solid barium sulfate is taken as a reference, and the test wavelength range is 190-800. The multi-coordination zirconium in the molecular sieve framework can generate an absorption peak at the wavelength of 240-280 nm, and the absorption peak of the zirconium oxide is less than 200 nm.
In the invention, the product composition is determined by gas chromatography, the chromatography model is Agilent 7890A, a FID detector is arranged, an FFAP capillary chromatographic column is used for separation, the temperature of the chromatographic column is programmed to be 90 ℃ initially, the chromatographic column is kept for 15 minutes, and then the temperature is increased to 220 ℃ at the speed of 15 ℃/minute and kept for 45 minutes.
The conversion X of 2-butene is calculated as:
X(2-butene)＝(MImport 2-butene-MOutlet 2-butene)/MImport 2-butene×100％
The selectivity Y of 1-butene is calculated by the formula:
Y(1-butene)＝M(Outlet 1-butene)/(MImport 2-butene-MOutlet 2-butene)×100％
The present invention is further illustrated by the following examples.
[ example 1 ]
6g of zirconium oxychloride is dissolved in isopropanol, and then the solution is added into 1000ml of ethyl orthosilicate to prepare a mixed solution I, and the mixed solution I is stirred for 50 minutes at room temperature. 2700ml of aqueous solution containing 10% tetrapropylammonium hydroxide was prepared to prepare solution II. 30g of alumina sol (40% of alumina content) was added to the solution II with stirring to obtain a feed solution III. Slowly adding the solution I into the feed liquid III under the stirring state, and adjusting the pH to 6 by using nitric acid and ammonia water to obtain feed liquid IV; after being uniformly stirred, the material liquid IV is placed in a crystallization kettle for aging for 20 hours at the temperature of 45 ℃, and then crystallized for 48 hours at the temperature of 170 ℃; and after crystallization, taking out, carrying out vacuum filtration, washing with deionized water, placing in an oven for drying at 120 ℃, and roasting at 550 ℃ for 4 hours to obtain the molecular sieve powder. The obtained molecular sieve is characterized by XRD and UV-vis, and the crystal form is ZSM-5/ZSM-11 eutectic molecular sieve containing framework zirconium.
70g of the molecular sieve, 30g of alumina, 60ml of 0.5 percent nitric acid and 5g of sesbania powder are kneaded and extruded into strips, the strips are baked for 4 hours at 120 ℃, and then the strips are baked for 4 hours at 500 ℃ to obtain the catalyst A1.
The results of the analytical tests are shown in Table 1.
[ example 2 ]
Take 70g of molecular sieve and 75ml of silica sol (containing 40% SiO%2) Kneading with 5g sesbania powder, extruding into strips, baking at 120 ℃ for 4 hours, and baking at 500 ℃ for 4 hours to obtain the catalyst A2.
The results of the analytical tests are shown in Table 1.
[ example 3 ]
Taking 50g of molecular sieve, 50g of alumina, 60ml of 0.5 percent nitric acid and 5g of sesbania powder, kneading, extruding, drying at 120 ℃ for 4 hours, and roasting at 500 ℃ for 4 hours to obtain the catalyst A3.
The results of the analytical tests are shown in Table 1.
[ example 4 ]
42g of molecular sieve, 58g of alumina, 60ml of 0.5 percent nitric acid and 5g of sesbania powder are taken to be kneaded, extruded into strips, baked for 4 hours at 120 ℃, and baked for 4 hours at 500 ℃ to obtain the catalyst A4.
The results of the analytical tests are shown in Table 1.
[ example 5 ]
31g of molecular sieve, 69g of alumina, 60ml of 0.5% nitric acid and 5g of sesbania powder are kneaded, extruded into strips, baked at 120 ℃ for 4 hours, and baked at 500 ℃ for 4 hours to obtain a catalyst A5 (example 1).
The results of the analytical tests are shown in Table 1.
[ example 6 ]
Taking 85g of molecular sieve, 15g of alumina, 60ml of 0.5 percent nitric acid and 5g of sesbania powder, kneading, extruding, drying at 120 ℃ for 4 hours, and roasting at 500 ℃ for 4 hours to obtain the catalyst A6.
The results of the analytical tests are shown in Table 1.
[ example 7 ]
1g of zirconium oxychloride is dissolved in isopropanol, and then added into 1000ml of ethyl orthosilicate to prepare a mixed solution I, and the mixed solution I is stirred for 50 minutes at room temperature. 2700ml of aqueous solution containing 10% tetrapropylammonium hydroxide was prepared to prepare solution II. 30g of alumina sol (40% of alumina content) was added to the solution II with stirring to obtain a feed solution III. Slowly adding the solution I into the feed liquid III under the stirring state, and adjusting the pH to 6 by using nitric acid and ammonia water to obtain feed liquid IV; after being uniformly stirred, the material liquid IV is placed in a crystallization kettle for aging for 20 hours at the temperature of 45 ℃, and then crystallized for 48 hours at the temperature of 170 ℃; and after crystallization, taking out, carrying out vacuum filtration, washing with deionized water, placing in an oven for drying at 120 ℃, and roasting at 550 ℃ for 4 hours to obtain the molecular sieve powder. The obtained molecular sieve is characterized by XRD and UV-vis, and the crystal form is ZSM-5/ZSM-11 eutectic molecular sieve containing framework zirconium.
70g of the molecular sieve, 30g of alumina, 60ml of 0.5 percent nitric acid and 5g of sesbania powder are kneaded and extruded into strips, the strips are baked for 4 hours at 120 ℃, and then the strips are baked for 4 hours at 500 ℃ to obtain the catalyst A7.
The results of the analytical tests are shown in Table 1.
[ example 8 ]
4g of zirconium oxychloride is dissolved in isopropanol, and then the solution is added into 1000ml of ethyl orthosilicate to prepare a mixed solution I, and the mixed solution I is stirred for 50 minutes at room temperature. 2700ml of aqueous solution containing 10% tetrapropylammonium hydroxide was prepared to prepare solution II. 30g of alumina sol (40% of alumina content) was added to the solution II with stirring to obtain a feed solution III. Slowly adding the solution I into the feed liquid III under the stirring state, and adjusting the pH to 6 by using nitric acid and ammonia water to obtain feed liquid IV; after being uniformly stirred, the material liquid IV is placed in a crystallization kettle for aging for 20 hours at the temperature of 45 ℃, and then crystallized for 48 hours at the temperature of 170 ℃; and after crystallization, taking out, carrying out vacuum filtration, washing with deionized water, placing in an oven for drying at 120 ℃, and roasting at 550 ℃ for 4 hours to obtain the molecular sieve powder. The obtained molecular sieve is characterized by XRD and UV-vis, and the crystal form is ZSM-5/ZSM-11 eutectic molecular sieve containing framework zirconium.
70g of the molecular sieve, 30g of alumina, 60ml of 0.5 percent nitric acid and 5g of sesbania powder are kneaded and extruded into strips, the strips are baked for 4 hours at 120 ℃, and then the strips are baked for 4 hours at 500 ℃ to obtain the catalyst A8.
The results of the analytical tests are shown in Table 1.
[ example 9 ]
23g of zirconium oxychloride is dissolved in isopropanol, and then added to 1000ml of ethyl orthosilicate to prepare a mixed solution I, and the mixed solution I is stirred at room temperature for 50 minutes. 2700ml of aqueous solution containing 10% tetrapropylammonium hydroxide was prepared to prepare solution II. 30g of alumina sol (40% of alumina content) was added to the solution II with stirring to obtain a feed solution III. Slowly adding the solution I into the feed liquid III under the stirring state, and adjusting the pH to 6 by using nitric acid and ammonia water to obtain feed liquid IV; after being uniformly stirred, the material liquid IV is placed in a crystallization kettle for aging for 20 hours at the temperature of 45 ℃, and then crystallized for 48 hours at the temperature of 170 ℃; and after crystallization, taking out, carrying out vacuum filtration, washing with deionized water, placing in an oven for drying at 120 ℃, and roasting at 550 ℃ for 4 hours to obtain the molecular sieve powder. The obtained molecular sieve is characterized by XRD and UV-vis, and the crystal form is ZSM-5/ZSM-11 eutectic molecular sieve containing framework zirconium.
70g of the molecular sieve, 30g of alumina, 60ml of 0.5 percent nitric acid and 5g of sesbania powder are kneaded and extruded into strips, the strips are baked for 4 hours at 120 ℃, and then the strips are baked for 4 hours at 500 ℃ to obtain the catalyst A9.
The results of the analytical tests are shown in Table 1.
[ example 10 ]
6g of zirconium oxychloride is dissolved in isopropanol, and then the solution is added into 1000ml of ethyl orthosilicate to prepare a mixed solution I, and the mixed solution I is stirred for 50 minutes at room temperature. 2700ml of aqueous solution containing 10% tetrapropylammonium hydroxide was prepared to prepare solution II. 30g of alumina sol (40% of alumina content) was added to the solution II with stirring to obtain a feed solution III. Slowly adding the solution I into the feed liquid III under the stirring state, and adjusting the pH to 6 by using nitric acid and ammonia water to obtain feed liquid IV; after being uniformly stirred, the material liquid IV is placed in a crystallization kettle for aging for 20 hours at the temperature of 45 ℃, and then crystallized for 48 hours at the temperature of 170 ℃; and after crystallization, taking out, carrying out vacuum filtration, washing with deionized water, placing in an oven for drying at 120 ℃, and roasting at 550 ℃ for 4 hours to obtain the molecular sieve powder. The obtained molecular sieve is characterized by XRD and UV-vis, and the crystal form is ZSM-5/ZSM-11 eutectic molecular sieve containing framework zirconium.
70g of the molecular sieve, 30g of alumina, 1g of magnesium oxide, 60ml of 0.5 percent nitric acid and 5g of sesbania powder are kneaded and extruded into strips, the strips are baked for 4 hours at 120 ℃, and then the strips are baked for 4 hours at 500 ℃ to obtain the catalyst A10.
The results of the analytical tests are shown in Table 1.
[ example 11 ]
6g of zirconium oxychloride were dissolved in isopropanol and then added to 700ml of silica sol (containing 40% SiO)2) To prepare a mixed solution I, and stirring the mixed solution I for 50 minutes at room temperature. 2700ml of water solution containing 8% of n-butylamine is prepared to prepare solution II. 10g of aluminum hydroxide was added to the solution II with stirring to obtain a feed liquid III. Slowly adding the solution I into the feed liquid III under the stirring state, and adjusting the pH to 6 by using nitric acid and ammonia water to obtain feed liquid IV; after being uniformly stirred, the material liquid IV is placed in a crystallization kettle for aging for 20 hours at the temperature of 45 ℃, and then crystallized for 50 hours at the temperature of 165 ℃; and after crystallization, taking out, carrying out vacuum filtration, washing with deionized water, placing in an oven for drying at 120 ℃, and roasting at 550 ℃ for 4 hours to obtain molecular sieve powder Z1. The obtained molecular sieve is characterized by XRD and UV-vis, and the crystal form is ZSM-5 type molecular sieve containing framework zirconium.
6g of zirconium oxychloride were dissolved in isopropanol and then added to 700ml of silica sol (containing 40% SiO)2) To prepare a mixed solution I, and stirring the mixed solution I for 50 minutes at room temperature. 2700ml of an aqueous solution containing 8% tetrabutylammonium bromide was prepared to prepare a solution II. 10g of aluminum hydroxide was added to the solution II with stirring to obtain a feed liquid III. Then stirredSlowly adding the solution I into the feed liquid III under the state, and adjusting the pH to 4 by using nitric acid and ammonia water to obtain feed liquid IV; after being uniformly stirred, the material liquid IV is placed in a crystallization kettle for aging for 20 hours at the temperature of 45 ℃, and then crystallized for 48 hours at the temperature of 135 ℃; and after crystallization, taking out, carrying out vacuum filtration, washing with deionized water, placing in an oven for drying at 120 ℃, and roasting at 550 ℃ for 4 hours to obtain molecular sieve powder Z2. The obtained molecular sieve is characterized by XRD and UV-vis, and the crystal form is ZSM-11 type molecular sieve containing framework zirconium.
35g of each of the molecular sieves Z1 and Z2, 30g of alumina, 60ml of 0.5 percent nitric acid and 5g of sesbania powder are kneaded and extruded into strips, the strips are dried for 4 hours at 120 ℃, and then the strips are roasted for 4 hours at 500 ℃ to obtain the catalyst A11.
The results of the analytical tests are shown in Table 1.
[ example 12 ]
6g of zirconium oxychloride is dissolved in isopropanol, and then the solution is added into 1000ml of ethyl orthosilicate to prepare a mixed solution I, and the mixed solution I is stirred for 50 minutes at room temperature. 2700ml of aqueous solution containing 11% tetramethylethylenediamine was prepared to prepare solution II. And adding 50g of aluminum sulfate into the solution II under the stirring state to obtain a feed liquid III. Slowly adding the solution I into the feed liquid III under the stirring state, and adjusting the pH to 6 by using nitric acid and ammonia water to obtain feed liquid IV; after being uniformly stirred, the material liquid IV is placed in a crystallization kettle for aging for 20 hours at the temperature of 45 ℃ and then crystallized for 48 hours at the temperature of 180 ℃; and after crystallization, taking out, carrying out vacuum filtration, washing with deionized water, placing in an oven for drying at 120 ℃, and roasting at 550 ℃ for 4 hours to obtain the molecular sieve powder. The obtained molecular sieve is characterized by XRD and UV-vis, and the crystal form is ZSM-5/ZSM-35 eutectic molecular sieve containing framework zirconium.
70g of the molecular sieve, 30g of alumina, 60ml of 0.5 percent nitric acid and 5g of sesbania powder are kneaded and extruded into strips, the strips are baked for 4 hours at 120 ℃, and then the strips are baked for 4 hours at 500 ℃ to obtain the catalyst A12.
The results of the analytical tests are shown in Table 1.
[ example 13 ]
The Zr-ZSM-5 molecular sieve was prepared by the method described in example 11, taking 70g of the above molecular sieve, 30g of alumina, 60ml of 0.5% nitric acid and 5g of sesbania powder, kneading, extruding, baking at 120 ℃ for 4 hours, and then baking at 500 ℃ for 4 hours to obtain catalyst A13.
[ example 14 ]
The Zr-ZSM-11 molecular sieve was prepared by the method described in example 11, taking 70g of the above molecular sieve, 30g of alumina, 60ml of 0.5% nitric acid and 5g of sesbania powder, kneading, extruding, baking at 120 ℃ for 4 hours, and then baking at 500 ℃ for 4 hours to obtain catalyst A14.
[ example 15 ]
6g of zirconium oxychloride are dissolved in isopropanol and then added to 700ml (containing 40% SiO)2) To prepare a mixed solution I, and stirring the mixed solution I for 50 minutes at room temperature. 2700ml of 11% cyclohexylamine-containing aqueous solution is prepared to prepare solution II. And adding 40g of aluminum sulfate into the solution II under the stirring state to obtain a feed liquid III. Slowly adding the solution I into the feed liquid III under the stirring state, and adjusting the pH to 6 by using nitric acid and ammonia water to obtain feed liquid IV; after being uniformly stirred, the material liquid IV is placed in a crystallization kettle for aging for 20 hours at the temperature of 45 ℃ and then crystallized for 48 hours at the temperature of 180 ℃; and after crystallization, taking out, carrying out vacuum filtration, washing with deionized water, placing in an oven for drying at 120 ℃, and roasting at 550 ℃ for 4 hours to obtain the molecular sieve powder. The obtained molecular sieve is characterized by XRD and UV-vis, and the crystal form of the molecular sieve is ZSM-35 molecular sieve containing framework zirconium.
70g of the molecular sieve, 30g of alumina, 60ml of 0.5 percent nitric acid and 5g of sesbania powder are kneaded and extruded into strips, the strips are baked for 4 hours at 120 ℃, and then the strips are baked for 4 hours at 500 ℃ to obtain the catalyst A15. The results of the analytical tests are shown in Table 1.
[ example 16 ]
6g of zirconium oxychloride are dissolved in isopropanol and then added to 700ml (containing 40% SiO)2) To prepare a mixed solution I, and stirring the mixed solution I for 50 minutes at room temperature. 2700ml of an aqueous solution containing 4% of n-propylamine and 8% of hexamethylenetetramine (R2) was prepared to prepare a solution II. And adding 5g of aluminum sulfate into the solution II under the stirring state to obtain a feed liquid III. Slowly adding the solution I into the feed liquid III under the stirring state, and adjusting the pH value to 4 by using sulfuric acid to obtain feed liquid IV; after being uniformly stirred, the material liquid IV is placed in a crystallization kettle for aging for 20 hours at the temperature of 60 ℃, and then crystallized for 130 hours at the temperature of 180 ℃; and after crystallization, taking out, carrying out vacuum filtration, washing with deionized water, placing in an oven for drying at 120 ℃, and roasting at 550 ℃ for 4 hours to obtain the molecular sieve powder. The obtained molecular sieve is characterized by XRD and UV-vis, and the crystal form is containing skeleton zirconiumZSM-39 molecular sieve.
70g of the molecular sieve, 30g of alumina, 60ml of 0.5 percent nitric acid and 5g of sesbania powder are kneaded and extruded into strips, the strips are baked for 4 hours at 120 ℃, and then the strips are baked for 4 hours at 500 ℃ to obtain the catalyst A16.
The results of the analytical tests are shown in Table 1.
[ COMPARATIVE EXAMPLE 1 ]
According to the preparation method of example 1, but a zirconium source is not added in the hydrothermal synthesis molecular sieve stage, and zirconium oxide is added in the later forming process. 1000ml of ethyl orthosilicate is prepared into a mixed solution I, and the mixed solution I is stirred for 50 minutes at room temperature. 2700ml of aqueous solution containing 10% tetrapropylammonium hydroxide was prepared to prepare solution II. 30g of alumina sol (40% of alumina content) was added to the solution II with stirring to obtain a feed solution III. Slowly adding the solution I into the feed liquid III under the stirring state, and adjusting the pH to 6 by using nitric acid and ammonia water to obtain feed liquid IV; after being uniformly stirred, the material liquid IV is placed in a crystallization kettle for aging for 20 hours at the temperature of 45 ℃, and then crystallized for 48 hours at the temperature of 170 ℃; and after crystallization, taking out, carrying out vacuum filtration, washing with deionized water, placing in an oven for drying at 120 ℃, and roasting at 550 ℃ for 4 hours to obtain the molecular sieve powder.
70g of the molecular sieve, 30g of alumina, 0.21g of zirconia, 60ml of 0.5 percent nitric acid and 5g of sesbania powder are kneaded and extruded into strips, the strips are dried for 4 hours at 120 ℃, and then the strips are roasted for 4 hours at 500 ℃ to obtain the catalyst B1.
The results of the analytical tests are shown in Table 1.
[ COMPARATIVE EXAMPLE 2 ]
The preparation was as per [ example 1 ], but no zirconium source was added during the hydrothermal synthesis of the molecular sieves. 1000ml of ethyl orthosilicate is prepared into a mixed solution I, and the mixed solution I is stirred for 50 minutes at room temperature. 2700ml of aqueous solution containing 10% tetrapropylammonium hydroxide was prepared to prepare solution II. 30g of alumina sol (40% of alumina content) was added to the solution II with stirring to obtain a feed solution III. Slowly adding the solution I into the feed liquid III under the stirring state, and adjusting the pH to 6 by using nitric acid and ammonia water to obtain feed liquid IV; after being uniformly stirred, the material liquid IV is placed in a crystallization kettle for aging for 20 hours at the temperature of 45 ℃, and then crystallized for 48 hours at the temperature of 170 ℃; and after crystallization, taking out, carrying out vacuum filtration, washing with deionized water, placing in an oven for drying at 120 ℃, and roasting at 550 ℃ for 4 hours to obtain the molecular sieve powder.
70g of the molecular sieve, 30g of alumina, 60ml of 0.5 percent nitric acid and 5g of sesbania powder are kneaded and extruded into strips, the strips are baked for 4 hours at 120 ℃, and then the strips are baked for 4 hours at 500 ℃ to obtain the catalyst B1.
The results of the analytical tests are shown in Table 1.
TABLE 1
Figure BDA0001823575470000151
[ example 17 ]
Examine [ examples 1-16 ] the use of catalysts in butene double bond isomerization reactions.
The catalysts of the present invention [ examples 1 to 16 ] were used for evaluation of the reaction. The raw material comprises 12.1% of n-butane, 35.6% of cis-2-butene and 51.3% of trans-2-butene mixed C4. At the reaction temperature of 250 ℃, the reaction pressure of 0.4MPa and the weight space velocity of 5 hours-1The catalysts were evaluated under the conditions and the reaction results are shown in Table 2.
[ COMPARATIVE EXAMPLE 3 ]
The catalysts obtained in comparative examples 1 and 1 were used for evaluation of the reaction. The mixed C4 containing n-butane 12.1%, cis-2-butene 35.6% and trans-2-butene 51.3% is used as raw material. The catalyst was evaluated at a reaction temperature of 250 ℃ and a reaction pressure of 0.4MPa at a weight space velocity of 5 hr-1, and the reaction results are shown in Table 2.
TABLE 2
Catalyst and process for preparing same 2-butene conversion% N-butene selectivity,%
A1 16.78 99.84
A2 16.69 99.83
A3 16.35 99.65
A4 16.18 99.49
A5 15.91 99.47
A6 16.54 99.21
A7 15.76 99.27
A8 16.56 99.78
A9 16.43 99.25
A10 13.78 99.12
A11 15,68 99.14
A12 16.45 99.46
A13 15.98 99.56
A14 15.87 99.51
A15 16.07 99.03
A16 16.17 99.25
B1 12.35 98.77
B2 14.17 98.03
It can be seen that with the catalyst of the invention, both activity and selectivity are significantly higher than the comparative examples.
[ examples 18 to 24 ]
The catalyst obtained in the present invention [ example 1 ] was used for evaluation of reaction, and the reaction conditions and results were shown in Table 3.
TABLE 3
Figure BDA0001823575470000161

Claims (16)

1. The butene double bond isomerization catalyst comprises, by weight, 30-90 parts of Zr-ZSM molecular sieve and 10-70 parts of binder, wherein the weight parts of the Zr-ZSM molecular sieve and the binder are relative to the total weight parts of the Zr-ZSM molecular sieve and the binder; wherein Zr is present in the molecular sieve framework.
2. The butene double bond isomerization catalyst of claim 1, wherein the Zr-ZSM molecule screens one of the group consisting of Zr-ZSM-5, Zr-ZSM-11, Zr-ZSM-35 and Zr-ZSM-39.
3. The butene double bond isomerization catalyst of claim 2, wherein the Zr-ZSM molecule screens a mechanical mixture of at least two of the group consisting of Zr-ZSM-5, Zr-ZSM-11, Zr-ZSM-35 and Zr-ZSM-39.
4. The butene double bond isomerization catalyst according to claim 2, characterized in that the Zr-ZSM molecule screens eutectic molecular sieves of at least two of the group consisting of Zr-ZSM-5, Zr-ZSM-11, Zr-ZSM-35 and Zr-ZSM-39, preferably Zr-ZSM-5/ZSM-11 eutectic molecular sieves.
5. The butene double bond isomerization catalyst according to claim 1, wherein the binder is at least one selected from the group consisting of alumina and silica.
6. The butene double bond isomerization catalyst according to claim 1, characterized in that the catalyst comprises 40 to 80 parts of the Zr-ZSM molecular sieve and 20 to 60 parts of the binder, relative to the total parts by weight of the Zr-ZSM molecular sieve and the binder; preferably, the Zr-ZSM molecular sieve comprises 50-80 parts of Zr-ZSM molecular sieve and 20-50 parts of binder.
7. The butene double bond isomerization catalyst according to claim 1, wherein the Zr-ZSM molecular sieve has a Si/Zr molar ratio of 50 to 1000, preferably 100 to 500.
8. The butene double bond isomerization catalyst according to any one of claims 1 to 7, wherein the catalyst does not contain an alkaline earth metal element or an oxide thereof.
9. The butene double bond isomerization catalyst according to claim 8, characterized in that the alkaline earth metal element is at least one selected from the group consisting of magnesium, calcium, strontium and barium; in particular magnesium.
10. A butene double bond isomerization catalyst comprises, by weight, 30-90 parts of Zr-ZSM-5/ZSM-11 eutectic molecular sieve and 10-70 parts of a binder; wherein, the molar ratio of silicon to zirconium is 50-1000, preferably 100-500; zr exists in the eutectic molecular sieve framework.
11. A butene double bond isomerization process comprising the step of contacting a stream containing 2-butene with a catalyst as claimed in any one of claims 1 to 10 to obtain 1-butene.
12. The butene double bond isomerization process of claim 11, wherein the contact temperature is 150 to 280 ℃, the pressure is 0 to 1MPa, and the weight space velocity is 1 to 10 hours-1(ii) a The preferable contact temperature is 180-270 ℃, the pressure is 0.5-1 MPa, and the weight space velocity is 2-5 hours-1。
13. The double bond isomerization process of butene according to claim 11, wherein the stream containing 2-butene is derived from a mixed carbon four stream as a by-product of a refinery catalytic cracking unit, an ethylene plant steam cracking unit or a coal-to-olefin unit, preferably a carbon four stream obtained by removing 1, 3-butadiene and isobutene from a mixed carbon four stream as a by-product of a refinery catalytic cracking unit, an ethylene plant steam cracking unit or a coal-to-olefin unit.
14. The butene double bond isomerization process of claim 11 wherein the 2-butene containing stream is a mixture of 1-butene and 2-butene that does not meet thermodynamic equilibrium values.
15. The butene double bond isomerization process of claim 11, wherein the 2-butene-containing stream has a 1-butene mass concentration of less than 4% and a 2-butene mass concentration of greater than 45%.
16. The butene double bond isomerization process of claim 11 wherein the 2-butene-containing stream has a1, 3-butadiene mass concentration of less than 30 ppm.
CN201811175352.5A 2018-10-10 2018-10-10 Butene double bond isomerization catalyst and application thereof Pending CN111013639A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201811175352.5A CN111013639A (en) 2018-10-10 2018-10-10 Butene double bond isomerization catalyst and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201811175352.5A CN111013639A (en) 2018-10-10 2018-10-10 Butene double bond isomerization catalyst and application thereof

Publications (1)

Publication Number Publication Date
CN111013639A true CN111013639A (en) 2020-04-17

Family

ID=70191210

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201811175352.5A Pending CN111013639A (en) 2018-10-10 2018-10-10 Butene double bond isomerization catalyst and application thereof

Country Status (1)

Country Link
CN (1) CN111013639A (en)

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5198597A (en) * 1991-07-30 1993-03-30 Texaco Inc. Bimetallic catalysts for dehydroisomerization of N-butane to isobutene
CN1662478A (en) * 2002-06-18 2005-08-31 埃克森美孚化学专利公司 Method for isomerizing a mixed olefin feedstock to 1-olefin
CN101121623A (en) * 2006-08-11 2008-02-13 中国石油化工股份有限公司 Method for butylenes double-bond isomerization
CN102649676A (en) * 2011-02-25 2012-08-29 中国石油化工股份有限公司 Method for double bond isomerization of butene
US20130245348A1 (en) * 2010-03-15 2013-09-19 Total Research & Technology Feluy Production of propylene via simultaneous dehydration and skeletal isomerisation of isobutanol on acid catalysts followed by metathesis
US20150273450A1 (en) * 2014-03-28 2015-10-01 Exxonmobil Research And Engineering Company Synthesis of framework modified zsm-48 crystals

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5198597A (en) * 1991-07-30 1993-03-30 Texaco Inc. Bimetallic catalysts for dehydroisomerization of N-butane to isobutene
CN1662478A (en) * 2002-06-18 2005-08-31 埃克森美孚化学专利公司 Method for isomerizing a mixed olefin feedstock to 1-olefin
CN101121623A (en) * 2006-08-11 2008-02-13 中国石油化工股份有限公司 Method for butylenes double-bond isomerization
US20130245348A1 (en) * 2010-03-15 2013-09-19 Total Research & Technology Feluy Production of propylene via simultaneous dehydration and skeletal isomerisation of isobutanol on acid catalysts followed by metathesis
CN102649676A (en) * 2011-02-25 2012-08-29 中国石油化工股份有限公司 Method for double bond isomerization of butene
US20150273450A1 (en) * 2014-03-28 2015-10-01 Exxonmobil Research And Engineering Company Synthesis of framework modified zsm-48 crystals

Similar Documents

Publication Publication Date Title
Sushkevich et al. Ethanol conversion into butadiene over Zr-containing molecular sieves doped with silver
US10307737B2 (en) Transition metal-noble metal complex oxide catalyst for dehydrogenation prepared by one-pot synthesis and use thereof
KR101519409B1 (en) Zsm-5, its preparation and use in ethylbenzene dealkylation
US9713804B2 (en) Catalyst composition for the dehydrogenation of alkanes
EP2902362B1 (en) Sapo-34 molecular sieve and synthesis method thereof
TW201632463A (en) A method for the synthesis of a type of FER/MOR composite molecular sieve
EP3558869B1 (en) Process to convert synthesis gas to olefins using a bifunctional chromium / zinc oxide-sapo-34 catalyst
CN105312082A (en) SAPO-34/ZSM-5 composite molecular sieve, and preparation method application thereof
JP2019155361A (en) Ni-CONTAINING CATALYST FOR OLIGOMERIZATION OF OLEFIN
CN116685661A (en) Treatment of paraffinic naphtha with modified USY zeolite dehydrogenation catalyst
KR20200126984A (en) Catalyst systems useful for dehydrogenation reactions
US20200368734A1 (en) A composition comprising a mixed metal oxide and a molding comprising a zeolitic material having framework type cha and an alkaline earth metal
CN111013641A (en) Double bond isomerization catalyst and use thereof
RU2622035C1 (en) Catalyst of dehydration of paraffin hydrocarbons, method of its production and method for dehydrated hydrocarbons using this catalyst
US9174204B2 (en) Catalyst based on zeolite for producing olefins and for oligomerizing olefins
JP6446033B2 (en) Process for producing unsaturated hydrocarbons
JP7394950B2 (en) Zinc oxide modified MFI type zeolite and method for producing aromatic compounds using the same
CN111013639A (en) Butene double bond isomerization catalyst and application thereof
CN111018650B (en) Butene isomerization process
US20210114006A1 (en) Bi-functional catalyst for the production of olefins from synthesis gas
CN111018648A (en) Method for producing 1-butene by isomerizing 2-butene
CN111018649A (en) Method for producing 1-butene by isomerization
CN111018647A (en) Butene isomerization process
CN1274596C (en) Process for preparing metallic-ion-containing Si-P-Al molecular sieve
CN111013640A (en) Isomerization catalyst, preparation method and application thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
WD01 Invention patent application deemed withdrawn after publication
WD01 Invention patent application deemed withdrawn after publication

Application publication date: 20200417