CN111018649A - Method for producing 1-butene by isomerization - Google Patents

Method for producing 1-butene by isomerization Download PDF

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Publication number
CN111018649A
CN111018649A CN201811175356.3A CN201811175356A CN111018649A CN 111018649 A CN111018649 A CN 111018649A CN 201811175356 A CN201811175356 A CN 201811175356A CN 111018649 A CN111018649 A CN 111018649A
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zsm
butene
molecular sieve
catalyst
hours
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龚海燕
刘俊涛
孙凤侠
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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    • 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
    • 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
    • C07C2529/18—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type
    • 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

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention relates to a method for producing 1-butene by isomerization, which comprises the following steps of a) enabling a feed stream containing 2-butene to enter a first reaction zone and contact with a catalyst A to generate a stream I, B) enabling the stream I to enter at least one second reaction zone and contact with a catalyst B to generate a product stream containing 1-butene, wherein the catalyst A contains at least one selected from the group consisting of mordenite, β molecular sieve and ZSM molecular sieve, and the catalyst B contains a molecular sieve Sn-ZSM with framework tin.

Description

Method for producing 1-butene by isomerization
Technical Field
The invention relates to a method for producing 1-butene through isomerization.
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 prepared from raw materialsAnd separating the rows to obtain the product. 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 the 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-1Under the conditions of (1), a double bond isomerization reaction is carried out. And (3) sampling and analyzing the reacted gas at regular time, wherein the content of the 1-butene is 19.0-27.0%. When the reaction temperature is controlled to be lower (300-320 ℃), the content of isobutene serving as an impurity generated by the reaction is lower, the selectivity of 1-butene is higher, and the conversion rate is only 19%. When the reaction temperature is increased and the conversion rate is increased, the content of impurity isobutene in the product is obviously increased, particularly when the conversion rate reaches 24%, the content of isobutene reaches 0.5%, and the selectivity of 1-butene is obviously reduced.
As the isomerization of 2-butene to 1-butene is accompanied by other side reactions such as skeletal isomerization, dehydration and cracking, etc. in addition to butene double bond isomerization, the side reactions affect the selectivity of the reaction on 1-butene. Although a single type of catalyst can perform isomerization reaction under a wide range of conditions, conversion and selectivity cannot be taken into consideration when the reaction conditions are greatly changed.
Disclosure of Invention
The present inventors have assiduously studied on the basis of the prior art and, as a result, have accomplished the present invention by solving at least one of the aforementioned problems by adopting a technical solution of loading catalysts having different catalytic activities in divided regions.
In particular, the invention relates to a method for producing 1-butene through isomerization. The method comprises the following steps:
a) feeding a feed stream containing 2-butene into a first reaction zone to contact with a catalyst A to produce a stream I;
b) passing said stream I to at least one second reaction zone for contact with catalyst B to produce a product stream comprising 1-butene;
wherein the catalyst A contains at least one selected from the group consisting of mordenite, β molecular sieve and ZSM molecular sieve, and the catalyst B contains molecular sieve Sn-ZSM with framework tin.
According to one aspect of the invention, the catalyst A comprises 30-90 parts by weight of molecular sieve and 10-70 parts by weight of first binder, preferably comprises 40-80 parts by weight of molecular sieve and 20-60 parts by weight of first binder, and more preferably comprises 50-80 parts by weight of molecular sieve and 20-50 parts by weight of first binder; relative to the total parts by weight of the molecular sieve and the first binder.
According to one aspect of the invention, the ZSM molecule is screened for one of the group consisting of ZSM-5, ZSM-11, ZSM-35 and ZSM-39; preferably a mechanical mixture of at least two selected from the group consisting of ZSM-5, ZSM-11, ZSM-35 and ZSM-39; more preferably a eutectic molecular sieve of at least two selected from the group consisting of ZSM-5, ZSM-11, ZSM-35 and ZSM-39; most preferred is a ZSM-5/ZSM-11 eutectic molecular sieve.
According to one aspect of the invention, the catalyst B comprises 50-99 parts by weight of Sn-ZSM molecular sieve and 1-50 parts by weight of second binder, preferably 55-95 parts by weight of Sn-ZSM molecular sieve and 5-45 parts by weight of second binder; more preferably, the composite material comprises 60-90 parts of Sn-ZSM molecular sieve and 10-40 parts of second binder; relative to the total weight parts of the Sn-ZSM molecular sieve and the second binder.
According to one aspect of the invention, the Sn-ZSM molecule screens one of the group consisting of Sn-ZSM-5, Sn-ZSM-11, Sn-ZSM-35 and Sn-ZSM-39; preferably a mechanical mixture of at least two selected from the group consisting of Sn-ZSM-5, Sn-ZSM-11, Sn-ZSM-35 and Sn-ZSM-39; more preferably eutectic molecular sieves of at least two selected from the group consisting of Sn-ZSM-5, Sn-ZSM-11, Sn-ZSM-35 and Sn-ZSM-39; most preferred is Sn-ZSM-5/ZSM-11 eutectic molecular sieve.
According to an aspect of the present invention, the first binder and the second binder are each at least one selected from the group consisting of alumina and silica.
According to one aspect of the invention, the molar ratio of silicon to tin in the Sn-ZSM molecular sieve is 50-700, preferably 100-500.
According to an aspect of the present invention, the alkaline earth metal element or the oxide thereof is not contained in both of the catalyst a and the catalyst B.
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.
According to one aspect of the invention, the reaction temperature of the first reaction zone is 150-280 ℃, the reaction pressure is 0-1 MPa, and the weight space velocity is 1-10 hours-1(ii) a The preferable reaction 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 reaction temperature of the second reaction zone is 280-420 ℃, the pressure is 0-1 MPa, and the weight space velocity is 1-10 hours-1(ii) a The preferable contact temperature is 300-400 ℃, 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 reaction temperature of the first reaction zone is lower than the reaction temperature of the second reaction zone.
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.
According to one aspect of the invention, the weight ratio of the catalyst A to the catalyst B is 0.1 to 8:1, preferably 0.2 to 5:1, more preferably 0.5 to 4: 1.
The invention has the beneficial effects that:
according to the invention, the conversion rate of 2-butene and the selectivity of 1-butene can be simultaneously improved.
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.
The "first binder" and "second binder" in the present invention are only named for distinguishing the respective binders of the catalyst a and the catalyst B, and have no other meaning.
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 method for producing 1-butene through isomerization. The method comprises the following steps:
a) feeding a feed stream containing 2-butene into a first reaction zone to contact with a catalyst A to produce a stream I;
b) passing said stream I to at least one second reaction zone for contact with catalyst B to produce a product stream comprising 1-butene;
wherein the catalyst A contains at least one selected from the group consisting of mordenite, β molecular sieve and ZSM molecular sieve, and the catalyst B contains molecular sieve Sn-ZSM with framework tin.
According to the invention, the catalyst A comprises 30-90 parts of molecular sieve and 10-70 parts of first binder, preferably comprises 40-80 parts of molecular sieve and 20-60 parts of first binder, and more preferably comprises 50-80 parts of molecular sieve and 20-50 parts of first binder; relative to the total parts by weight of the molecular sieve and the first binder.
According to the invention, the catalyst A contains at least one selected from the group consisting of mordenite, β molecular sieve and ZSM molecular sieve, preferably ZSM molecular sieve, generally, the mordenite has a silicon-aluminum molar ratio of 10-60, preferably 20-50, more preferably 30-45, the β molecular sieve has a silicon-aluminum molar ratio of 20-120, preferably 30-100, more preferably 50-90. ZSM molecular sieve has a silicon-aluminum molar ratio of 50-500, preferably 100-450, more preferably 200-400, and the molecular sieve also comprises ion exchange forms of the molecular sieves.
According to the present invention, the ZSM molecular sieve may be one selected from the group consisting of ZSM-5, ZSM-11, ZSM-35 and ZSM-39; or a mechanical mixture of at least two selected from the group consisting of ZSM-5, ZSM-11, ZSM-35 and ZSM-39; or may be a eutectic molecular sieve of at least two selected from the group consisting of ZSM-5, ZSM-11, ZSM-35 and ZSM-39, preferably ZSM-5/ZSM-11 eutectic molecular sieve. The eutectic molecular sieve described herein, which is also referred to in the art as intergrown molecular sieve, is distinguished from a simple mechanical mixture by the fact that crystals of several morphologies aggregate with one another, a growing conglomerate, crystallize together, you in me.
According to the present invention, the first binder is at least one selected from the group consisting of alumina and silica.
According to an embodiment of the present invention, the catalyst a 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 the invention, the catalyst B comprises 50-99 parts by weight of Sn-ZSM molecular sieve and 1-50 parts by weight of second binder, preferably 55-95 parts by weight of Sn-ZSM molecular sieve and 5-45 parts by weight of second binder; more preferably, the composite material comprises 60-90 parts of Sn-ZSM molecular sieve and 10-40 parts of second binder; relative to the total weight parts of the Sn-ZSM molecular sieve and the second binder.
According to the invention, in the Sn-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 Si to Sn is 50 to 700, preferably 100 to 500.
According to the present invention, the Sn-ZSM molecular sieve may be one selected from the group consisting of Sn-ZSM-5, Sn-ZSM-11, Sn-ZSM-35, and Sn-ZSM-39; or a mechanical mixture of at least two selected from the group consisting of Sn-ZSM-5, Sn-ZSM-11, Sn-ZSM-35, and Sn-ZSM-39; or may be eutectic molecular sieves of at least two selected from the group consisting of Sn-ZSM-5, Sn-ZSM-11, Sn-ZSM-35 and Sn-ZSM-39, preferably Sn-ZSM-5/ZSM-11 eutectic molecular sieves. 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 second binder is at least one selected from the group consisting of alumina and silica.
According to an embodiment of the present invention, the catalyst B 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 the invention, the catalyst B 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 templating agent, a tin source, a silicon source, an aluminum source, and water to obtain a Sn-ZSM molecular sieve, and molding the Sn-ZSM molecular sieve with a second 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 tin source may use any tin source conventionally used in the art for this purpose, including but not limited to tin nitrate, tin tetrachloride and stannous oxalate, with tin nitrate and tin tetrachloride 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, aluminum sulfate 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 tin source (SnO)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 pH of the second mixture is controlled to 4 to 9, and any acid or base conventionally used in the art for this purpose may be used therefor, and examples thereof includeHydrochloric acid, nitric acid, sulfuric acid, NaOH, KOH, and ammonia.
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 Sn-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.
If necessary, the crystallized Sn-ZSM molecular sieve may be calcined to remove the organic template and water, etc. that may be present, thereby obtaining a calcined 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 Sn-ZSM molecular sieve with a second binder, and molding to obtain the catalyst B. The catalyst B 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 second 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 B 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 process of the catalyst B, the second 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.
According to the invention, the catalyst A contains at least one selected from the group consisting of mordenite, β molecular sieve and ZSM molecular sieve, so that the catalyst A is ensured to have higher activity, and according to the characteristic of the catalyst A, the reaction conditions of the first reaction zone are controlled at a lower reaction temperature, wherein the reaction temperature is 150-280 ℃, the reaction pressure is 0-1 MPa, and the weight space velocity is 1-20 hours-1(ii) a The preferable reaction temperature is 180-270 ℃, the pressure is 0.5-1 MPa, and the weight space velocity is 2-10 hours-1。
According to the invention, the catalyst B contains tin having a skeletonSn-ZSM of (1). Framework Sn may reduce the acidity of the molecular sieve. The second reaction zone is controlled at a higher reaction temperature according to this characteristic of the catalyst B. The reaction conditions of the second reaction zone include: the reaction temperature is 280-420 ℃, the pressure is 0-1 MPa, and the weight space velocity is 1-20 hours-1(ii) a The preferable contact temperature is 300-400 ℃, the pressure is 0.5-1 MPa, and the weight space velocity is 2-10 hours-1。
According to the invention, the weight ratio of the catalyst A to the catalyst B is 0.1-8: 1, preferably 0.2-5: 1, and more preferably 0.5-4: 1.
According to the invention, the two catalysts have different characteristics, the reaction temperature of the first reaction zone is low, most of raw material 2-butene is converted at low temperature through the high-activity catalyst A, and then the conversion rate is further improved through the reaction of the second reaction zone catalyst B at high temperature. Meanwhile, the catalyst A in the first reaction zone has relatively weak activity, so that side reactions are relatively less, and the effects of high conversion rate and high selectivity can be achieved simultaneously.
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 tin content in the catalyst under the following test conditions: an iCAP7600Duo inductively coupled plasma emission spectrometer of American Sammer Feishell company is adopted, metallic tin is adopted 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 phases of the catalyst A and the catalyst B are carried out 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 degree/min.
The existence form of Sn of the catalyst B is measured by a Cary5000 type ultraviolet-visible spectrometer, a white board is taken as a reference, and the test wavelength range is 190-800. The multi-site tin in the molecular sieve framework can generate an absorption peak at the wavelength of 210-220 nm, while the absorption peak of non-framework tin or tin oxide is at the wavelength of 260-320 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 ]
1) 1000ml of an ethyl orthosilicate solution I are prepared and 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 molecular sieve powder Z1-a. The crystal form of the obtained molecular sieve is ZSM-5/ZSM-11 eutectic molecular sieve by XRD.
70g of the Z1-a 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 dried for 4 hours at 120 ℃, and then the strips are roasted for 4 hours at 500 ℃ to obtain a catalyst A1, and the catalyst A1 is filled into a first reactor.
2) Tin tetrachloride (8.5 g) was dissolved in isopropanol, and then added to ethyl orthosilicate (1000 ml) to prepare a mixed solution I, which was 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 molecular sieve powder Z1-b. The obtained molecular sieve is characterized by XRD and UV-vis, and the crystal form is Sn-ZSM-5/ZSM-11 eutectic molecular sieve with framework tin.
70g of the Z1-B 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 dried for 4 hours at 120 ℃, and then are roasted for 4 hours at 500 ℃ to obtain a catalyst B1, and the catalyst B1 is filled into a second reactor.
The results of the catalyst analysis are shown in tables 1 and 2.
[ example 2 ]
1) Take [ example 1 ] molecular Sieve Z1-a 70g, silica sol 75ml (containing 40% SiO)2) Kneading with 5g sesbania powder, extruding into strips, baking at 120 ℃ for 4 hours, baking at 500 ℃ for 4 hours to obtain a catalyst A2, and filling into a first reactor.
2) Take [ example 1 ] molecular Sieve Z1-b 70g, silica sol 75ml (containing 40% SiO)2) Kneading with 5g sesbania powder, extruding, baking at 120 deg.C for 4 hr, baking at 500 deg.C for 4 hr to obtain catalyst B2, and loading into the second reactor.
The results of the analytical tests are shown in Table 1.
[ example 3 ]
1) Taking 50g of Z1-a molecular sieve, 50g of alumina, 60ml of 0.5 percent nitric acid and 5g of sesbania powder, kneading, extruding into strips, baking at 120 ℃ for 4 hours, baking at 500 ℃ for 4 hours to obtain a catalyst A3, and filling the catalyst A3 into a first reactor.
2) Taking 65g of Z1-B molecular sieve, 35g of alumina, 60ml of 0.5 percent nitric acid and 5g of sesbania powder, kneading, extruding into strips, baking at 120 ℃ for 4 hours, baking at 500 ℃ for 4 hours to obtain a catalyst B3, and filling the catalyst B3 into a second reactor.
The results of the analytical tests are shown in tables 1 and 2.
[ example 4 ]
1) 42g of Z1-a 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 at 120 ℃ for 4 hours and baked at 500 ℃ for 4 hours to obtain a catalyst A4, and the catalyst A4 is filled into a first reactor.
2) The catalyst B1 from [ example 1 ] was charged to the second reaction zone.
The results of the analytical tests are shown in tables 1 and 2.
[ example 5 ]
1) 31g of Z1-a molecular sieve, 69g of alumina, 60ml of 0.5 percent nitric acid and 5g of sesbania powder are taken to be kneaded, extruded into strips, baked at 120 ℃ for 4 hours and baked at 500 ℃ for 4 hours to obtain a catalyst A5, and the catalyst A5 is filled into a first reactor.
2) 57g of the molecular sieve Z1-B, 43g of alumina, 60ml of 0.5 percent nitric acid and 5g of sesbania powder are kneaded, extruded into strips, baked at 120 ℃ for 4 hours, baked at 500 ℃ for 4 hours to obtain the catalyst B5, and the catalyst B5 is filled into a second reactor.
The results of the analytical tests are shown in tables 1 and 2.
[ example 6 ]
1) Taking 85g of Z1-a molecular sieve, 15g of alumina, 60ml of 0.5 percent nitric acid and 5g of sesbania powder, kneading, extruding into strips, baking at 120 ℃ for 4 hours, baking at 500 ℃ for 4 hours to obtain a catalyst A6, and filling the catalyst A6 into a first reactor.
2) 51g of molecular sieve Z1-B, 49g of alumina, 60ml of 0.5% nitric acid and 5g of sesbania powder are kneaded, extruded into strips, baked at 120 ℃ for 4 hours, baked at 500 ℃ for 4 hours to obtain catalyst B6, and the catalyst B6 is filled into a second reactor.
The results of the analytical tests are shown in tables 1 and 2.
[ example 7 ]
1) 1000ml of ethyl orthosilicate was prepared as solution I and 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 molecular sieve powder Z7-a. The obtained molecular sieve is characterized by XRD, and the crystal form is ZSM-5/ZSM-11 eutectic molecular sieve.
70g of the Z7-a 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 dried for 4 hours at 120 ℃, and then the strips are roasted for 4 hours at 500 ℃ to obtain a catalyst A7, and the catalyst A7 is filled into a first reactor.
2) Taking 85g of Z1-B molecular sieve, 15g of alumina, 60ml of 0.5 percent nitric acid and 5g of sesbania powder, kneading, extruding into strips, baking at 120 ℃ for 4 hours, baking at 500 ℃ for 4 hours to obtain a catalyst B7, and filling the catalyst B7 into a second reactor.
The results of the analytical tests are shown in tables 1 and 2.
[ example 8 ]
1) 1000ml of ethyl orthosilicate was prepared as solution I and 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 molecular sieve powder Z8-a. The crystal form of the obtained molecular sieve is ZSM-5/ZSM-11 eutectic molecular sieve by XRD.
70g of the Z8-a 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 dried for 4 hours at 120 ℃, and then the strips are roasted for 4 hours at 500 ℃ to obtain a catalyst A8, and the catalyst A8 is filled into a first reactor.
2) 4g of tin tetrachloride was dissolved in isopropanol, and then added to 1000ml of ethyl orthosilicate to prepare a mixed solution I, which was 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 molecular sieve powder Z8-b. The obtained molecular sieve is characterized by XRD and UV-vis, and the crystal form is Sn-ZSM-5/ZSM-11 eutectic molecular sieve with framework tin.
70g of the Z8-B 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 dried for 4 hours at 120 ℃, and then are roasted for 4 hours at 500 ℃ to obtain a catalyst B8, and the catalyst B8 is filled into a second reactor.
The results of the analytical tests are shown in tables 1 and 2.
[ example 9 ]
1) 1000ml of ethyl orthosilicate was prepared as solution I and 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 molecular sieve powder Z9-a. The crystal form of the obtained molecular sieve is ZSM-5/ZSM-11 eutectic molecular sieve by XRD.
70g of the Z9-a 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 dried for 4 hours at 120 ℃, and then the strips are roasted for 4 hours at 500 ℃ to obtain a catalyst A9, and the catalyst A9 is filled into a first reactor.
2) 5.6g of tin tetrachloride was dissolved in isopropanol, and then added to 1000ml of ethyl orthosilicate to prepare a mixed solution I, which was 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 37 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 molecular sieve powder Z9-b. The obtained molecular sieve is characterized by XRD and UV-vis, and the crystal form is Sn-ZSM-5/ZSM-11 eutectic molecular sieve with framework tin.
70g of the Z9-B 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 dried for 4 hours at 120 ℃, and then are roasted for 4 hours at 500 ℃ to obtain a catalyst B9, and the catalyst B9 is filled into a second reactor.
The results of the analytical tests are shown in tables 1 and 2.
[ example 10 ]
1) Take [ example 8 ] A8 and charge it to the first reactor.
2) 37g of tin tetrachloride was dissolved in isopropanol, and then added to 1000ml of ethyl orthosilicate to prepare a mixed solution I, which was 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 Sn-ZSM-5/ZSM-11 eutectic molecular sieve with framework tin.
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 dried for 4 hours at 120 ℃, then the strips are roasted for 4 hours at 500 ℃, and a catalyst B10 is obtained, and the obtained product is loaded into a second reactor.
The results of the analytical tests are shown in tables 1 and 2.
[ example 11 ]
1) 1000ml of ethyl orthosilicate was prepared as solution I and 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 molecular sieve powder Z11-a. The obtained molecular sieve is characterized by XRD and UV-vis, and the crystal form is ZSM-5/ZSM-11 eutectic molecular sieve.
70g of the Z11-a 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 ℃, then the strips are baked for 4 hours at 500 ℃ to obtain a catalyst A11, and the catalyst A11 is filled into a first reactor.
2) B1 from [ example 1 ] was charged into the second reaction zone.
The results of the analytical tests are shown in tables 1 and 2.
[ example 12 ]
1) 700ml of silica sol (containing 40% SiO2) was taken as solution I and stirred at room temperature for 50 minutes. 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 Z12 a-1. The obtained molecular sieve is subjected to XRD and is a crystal form ZSM-5 type molecular sieve.
700ml of silica sol (containing 40% SiO2) was taken as solution I and stirred at room temperature for 50 minutes. 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. Slowly adding the solution I into the feed liquid III under the stirring 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 Z12 a-2. The obtained molecular sieve is subjected to XRD and is a crystal form ZSM-11 type molecular sieve.
35g of each of the molecular sieves Z12a-1 and Z12a-2, 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 at 120 ℃ for 4 hours and then baked at 500 ℃ for 4 hours to obtain a catalyst A12, and the catalyst A12 is filled into a first reactor.
2) 8.5g of tin 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 37 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 molecular sieve powder Z12 b. The obtained molecular sieve is characterized by XRD and UV-vis, and the crystal form is Sn-ZSM-5/ZSM-11 eutectic molecular sieve with framework tin.
70g of the Z12B 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 dried for 4 hours at 120 ℃, then the strips are roasted for 4 hours at 500 ℃ to obtain a catalyst B12, and the catalyst B12 is filled into a second reactor.
The results of the analytical tests are shown in tables 1 and 2.
[ example 13 ]
1) 1000ml of ethyl orthosilicate was taken as solution I and stirred at room temperature for 50 minutes. 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 molecular sieve powder Z13-a. The obtained molecular sieve is characterized by XRD, and the crystal form of the ZSM-5/ZSM-35 eutectic molecular sieve is obtained.
70g of the Z13-a 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 dried for 4 hours at 120 ℃, and then the strips are roasted for 4 hours at 500 ℃ to obtain a catalyst A13, and the catalyst A13 is filled into a first reactor.
2) After 8.5g of tin tetrachloride was dissolved in isopropanol, the resulting solution was added to 700ml of silica sol (containing 40% SiO2) to prepare a mixed solution I, which was stirred at room temperature for 50 minutes. 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 42 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 Z13 b-1. The obtained molecular sieve is characterized by XRD and UV-vis, and the crystal form of the molecular sieve is Sn-ZSM-5 type molecular sieve with framework tin.
After 8.5g of tin tetrachloride was dissolved in isopropanol, the resulting solution was added to 700ml of silica sol (containing 40% SiO2) to prepare a mixed solution I, which was stirred at room temperature for 50 minutes. 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. Slowly adding the solution I into the feed liquid III under the stirring 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 36 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 Z13 b-2. The obtained molecular sieve is characterized by XRD and UV-vis, and the crystal form of the molecular sieve is Sn-ZSM-11 type molecular sieve with framework tin.
35g of each of the molecular sieves Z13B-1 and Z13B-2, 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 at 120 ℃ for 4 hours and then baked at 500 ℃ for 4 hours to obtain a catalyst B13, and the catalyst B13 is loaded into a second reactor.
The results of the analytical tests are shown in tables 1 and 2.
[ example 14 ]
1) ZSM-5 molecular sieve Z12a-1 was prepared by the method of [ example 12 ], and 70g of the molecular sieve Z12a-1, 30g of alumina, 60ml of 0.5% nitric acid and 5g of sesbania powder were kneaded, extruded into strips, baked at 120 ℃ for 4 hours, and then baked at 500 ℃ for 4 hours to obtain catalyst A14, which was then loaded into the first reactor.
2) Tin tetrachloride (8.5 g) was dissolved in isopropanol, and then added to ethyl orthosilicate (1000 ml) to prepare a mixed solution I, which was stirred at room temperature for 50 minutes. 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 42 hours at the temperature of 175 ℃; 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 Z14-b. The obtained molecular sieve is characterized by XRD and UV-vis, and the crystal form of the molecular sieve is Sn-ZSM-5/35 eutectic molecular sieve with framework tin.
70g of the Z14-B 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 dried for 4 hours at 120 ℃, and then are roasted for 4 hours at 500 ℃ to obtain a catalyst B14, and the catalyst B14 is filled into a second reactor.
The results of the analytical tests are shown in Table 1.
[ example 15 ]
1) ZSM-11 molecular sieve Z12a-2 was prepared by the method of [ example 12 ], and 70g of the above molecular sieve, 30g of alumina, 60ml of 0.5% nitric acid and 5g of sesbania powder were kneaded, extruded into strips, baked at 120 ℃ for 4 hours, and then baked at 500 ℃ for 4 hours to obtain catalyst A15, which was loaded into the first reactor.
2) Preparing Sn-ZSM-5 molecular sieve Z13B-1 by the method of [ example 13 ], kneading 70g of the molecular sieve, 30g of alumina, 60ml of 0.5% nitric acid and 5g of sesbania powder, extruding into strips, baking at 120 ℃ for 4 hours, baking at 500 ℃ for 4 hours to obtain catalyst B15, and filling the catalyst B15 into a second reactor.
The results of the analytical tests are shown in tables 1 and 2.
[ example 16 ]
1) 700ml (containing 40% SiO2) were taken as solution I and stirred 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 molecular sieve powder Z16-a. The obtained molecular sieve is characterized by XRD, and the crystal form is ZSM-35 molecular sieve.
70g of the Z16-a 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.
2) Preparing a Sn-ZSM-11 molecular sieve Z13B-2 by the method of [ example 13 ], kneading 70g of the molecular sieve, 30g of alumina, 60ml of 0.5% nitric acid and 5g of sesbania powder, extruding into strips, baking at 120 ℃ for 4 hours, baking at 500 ℃ for 4 hours to obtain a catalyst B16, and filling the catalyst B16 into a second reactor.
The results of the analytical tests are shown in tables 1 and 2.
[ example 17 ]
1) 700ml (containing 40% SiO2) were taken as solution I and stirred 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 molecular sieve powder Z17-a. The crystal form of the obtained molecular sieve is ZSM-39 molecular sieve by XRD.
70g of the Z17-a 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 dried for 4 hours at 120 ℃, and then the strips are roasted for 4 hours at 500 ℃ to obtain a catalyst A17, and the catalyst A17 is filled into a first reactor.
2) After 8.5g of tin tetrachloride was dissolved in isopropanol, 700ml (containing 40% SiO2) was added to prepare a mixed solution I, which was then stirred at room temperature for 50 minutes. 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 molecular sieve powder Z17-b. The obtained molecular sieve is characterized by XRD and UV-vis, and the crystal form of the molecular sieve is Sn-ZSM-35 molecular sieve with framework tin.
70g of the Z17-B 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 dried for 4 hours at 120 ℃, and then are roasted for 4 hours at 500 ℃ to obtain a catalyst B17, and the catalyst B17 is filled into a second reactor.
The results of the analytical tests are shown in tables 1 and 2.
[ example 18 ]
1) Catalyst a1 was charged to the first reaction zone [ example 1 ].
2) After 8.5g of tin tetrachloride was dissolved in isopropanol, 700ml (containing 40% SiO2) was added to prepare a mixed solution I, which was then stirred at room temperature for 50 minutes. 2700ml of aqueous solution containing 4% of n-propylamine and 8% of hexamethylenetetramine is prepared to prepare 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 140 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 molecular sieve powder Z18-b. The obtained molecular sieve is characterized by XRD and UV-vis, and the crystal form of the molecular sieve is Sn-ZSM-39 molecular sieve with framework tin.
70g of the Z18-B 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 dried for 4 hours at 120 ℃, and then are roasted for 4 hours at 500 ℃ to obtain a catalyst B18, and the catalyst B18 is filled into a second reactor.
The results of the analytical tests are shown in tables 1 and 2.
[ example 19 ]
1) 70g of commercial β molecular sieve, 30g of alumina, 60ml of 0.5% nitric acid and 5g of sesbania powder are kneaded and extruded into strips, the strips are baked for 4 hours at 120 ℃, then the strips are baked for 4 hours at 500 ℃ to obtain a catalyst A19, and the catalyst A19 is filled into a first reactor.
2) B1 from [ example 1 ] was charged into the second reaction zone.
The results of the analytical tests are shown in tables 1 and 2.
[ example 20 ]
1) 700ml (containing 40% SiO2) were taken as solution I and stirred for 50 minutes at room temperature. 300ml of an aqueous solution containing 3% hexadecyltrimethylammonium bromide was prepared to prepare a solution II. And adding 40g of sodium metaaluminate 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 9 by using sodium hydroxide to obtain feed liquid IV; after being uniformly stirred, the material liquid IV is placed in a crystallization kettle to be aged for 12 hours at the temperature of 100 ℃, and then crystallized for 48 hours at the temperature of 130 ℃; 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 Z20-a. The crystal form of the obtained molecular sieve is mordenite molecular sieve by XRD.
70g of the Z20-a 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 dried for 4 hours at 120 ℃, and then the strips are roasted for 4 hours at 500 ℃ to obtain a catalyst A20, and the catalyst A20 is filled into a first reactor.
2) B1 from [ example 1 ] was charged into the second reaction zone.
The results of the analytical tests are shown in tables 1 and 2.
[ COMPARATIVE EXAMPLE 1 ]
[ example 1 ] catalyst A1 was charged into the first and second reaction zones, respectively.
The results of the analytical tests are shown in tables 1 and 2.
[ COMPARATIVE EXAMPLE 2 ]
[ example 1 ] catalyst B1 was charged into the first and second reaction zones, respectively.
The results of the analytical tests are shown in tables 1 and 2.
[ example 21 ]
Examine [ examples 1-20 ] the application of A/B two catalysts in butene double bond isomerization reaction.
The catalysts of the present invention [ examples 1 to 20 ] were charged into the first and second reaction zones, respectively, in the manner shown in Table 1 to conduct reaction evaluation. The raw material comprises 12.1% of n-butane, 35.6% of cis-2-butene and 51.3% of trans-2-butene mixed C4. The catalyst was evaluated under the conditions of a temperature of 250 ℃ in the reactor I, a reaction pressure of 0.4MPa, a weight space velocity of 8 hr-1, a temperature of 350 ℃ in the reactor II, a reaction pressure of 0.4MPa, and a weight space velocity of 8 hr-1, and the reaction results are shown in Table 3.
[ COMPARATIVE EXAMPLE 3 ]
The respective first and second reaction zones were charged in the manner as described in Table 1 of the catalyst to conduct 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. The catalyst was evaluated under the conditions of a temperature of 250 ℃ in the reactor I, a reaction pressure of 0.4MPa, a weight space velocity of 8 hr-1, a temperature of 350 ℃ in the reactor II, a reaction pressure of 0.4MPa, and a weight space velocity of 10 hr-1, and the reaction results are shown in Table 3.
TABLE 1
Figure BDA0001823576260000211
TABLE 2
Figure BDA0001823576260000221
TABLE 3
Catalyst loading 2-butene conversion% 1-butene selectivity,%)
Example 1 21.98 99.30
Example 2 22.08 99.20
Example 3 21.98 99.10
Example 4 21.68 99.10
Example 5 21.48 99.00
Example 6 22.08 98.80
Example 7 21.58 99.10
Example 8 22.08 98.90
Example 9 22.08 98.70
Example 10 21.58 99.30
Example 11 19.60 99.20
Example 12 19.50 99.10
Example 13 21.68 99.00
Example 14 21.88 98.90
Example 15 22.08 98.80
Example 16 21.98 98.90
Example 17 22.08 99.00
Example 18 22.08 98.90
Example 19 21.68 99.00
Example 20 22.08 98.10
Comparative example 1 21.88 98.20
Comparative example 2 19.88 94.35
[ examples 22 to 28 ]
The catalysts a1 and B1 obtained in the present invention [ example 1 ] were subjected to reaction evaluation in the manner of [ example 21 ], and tests were carried out while changing the process conditions, and the reaction conditions and results are shown in table 4.
TABLE 4
Figure BDA0001823576260000241
[ COMPARATIVE EXAMPLE 4 ]
The first reaction zone is SiO by the method disclosed in the document CN102649671A2/Al2O3The molar ratio is 200 and the second reaction zone is silica.
The raw material comprises 12.1% of n-butane, 35.6% of cis-2-butene and 51.3% of trans-2-butene mixed C4. The temperature of the first reaction zone is controlled to be 320 ℃, the reaction pressure is 0.8MPa, and the weight space velocity is 20 hours-1The temperature of the second reaction zone is 340 ℃, the reaction pressure is 0.5MPa, and the weight space velocity is 10 hours-1The catalyst was evaluated under the conditions and the reaction results were: the 2-butene conversion was 23.2% and the 1-butene selectivity was only 97.1%.
The degree of conversion of 2-butene in the first reaction zone is higher and the amount of 2-butene participating in the reaction in the second reaction zone is smaller, compared to [ comparative example 4 ], so that the reaction severity in the second reaction zone is lower. Meanwhile, the molecular sieve Sn-ZSM with the framework tin in the second reaction zone not only keeps the activity of the catalyst, but also controls strong active sites, so that the catalyst can keep good 1-butene selectivity at high temperature.

Claims (17)

1. A process for the isomerization production of 1-butene comprising the steps of:
a) feeding a feed stream containing 2-butene into a first reaction zone to contact with a catalyst A to produce a stream I;
b) passing said stream I to at least one second reaction zone for contact with catalyst B to produce a product stream comprising 1-butene;
wherein the catalyst A contains at least one selected from the group consisting of mordenite, β molecular sieve and ZSM molecular sieve, and the catalyst B contains molecular sieve Sn-ZSM with framework tin.
2. The isomerization process for producing 1-butene according to claim 1, wherein the catalyst A comprises 30 to 90 parts by weight of molecular sieve and 10 to 70 parts by weight of first binder, preferably comprises 40 to 80 parts by weight of molecular sieve and 20 to 60 parts by weight of first binder, and more preferably comprises 50 to 80 parts by weight of molecular sieve and 20 to 50 parts by weight of first binder; relative to the total parts by weight of the molecular sieve and the first binder.
3. The isomerization process for producing 1-butene according to claim 1 wherein the ZSM molecule is screened for one of the group consisting of ZSM-5, ZSM-11, ZSM-35 and ZSM-39; preferably a mechanical mixture of at least two selected from the group consisting of ZSM-5, ZSM-11, ZSM-35 and ZSM-39; more preferably a eutectic molecular sieve of at least two selected from the group consisting of ZSM-5, ZSM-11, ZSM-35 and ZSM-39; most preferred is a ZSM-5/ZSM-11 eutectic molecular sieve.
4. The isomerization process for producing 1-butene according to claim 1, wherein the catalyst B comprises 50 to 99 parts by weight of Sn-ZSM molecular sieve and 1 to 50 parts by weight of second binder, preferably 55 to 95 parts by weight of Sn-ZSM molecular sieve and 5 to 45 parts by weight of second binder; more preferably, the composite material comprises 60-90 parts of Sn-ZSM molecular sieve and 10-40 parts of second binder; relative to the total weight parts of the Sn-ZSM molecular sieve and the second binder.
5. The isomerization process for producing 1-butene according to claim 1 or 4 wherein the Sn-ZSM molecule is screened for one of the group consisting of Sn-ZSM-5, Sn-ZSM-11, Sn-ZSM-35 and Sn-ZSM-39; preferably a mechanical mixture of at least two selected from the group consisting of Sn-ZSM-5, Sn-ZSM-11, Sn-ZSM-35 and Sn-ZSM-39; more preferably eutectic molecular sieves of at least two selected from the group consisting of Sn-ZSM-5, Sn-ZSM-11, Sn-ZSM-35 and Sn-ZSM-39; most preferred is Sn-ZSM-5/ZSM-11 eutectic molecular sieve.
6. The process for the production of 1-butene according to claim 2 or 4 wherein said first binder and said second binder are both selected from at least one of the group consisting of alumina and silica.
7. The isomerization process for producing 1-butene according to any one of claims 1 and 4 to 6, wherein the molar ratio of Si to Sn in the Sn-ZSM molecular sieve is 50 to 700, preferably 100 to 500.
8. The process for the production of 1-butene according to any one of claims 1 to 7 wherein neither said catalyst A nor said catalyst B comprises an alkaline earth metal element or an oxide thereof.
9. The process for producing 1-butene according to claim 8, wherein the alkaline earth metal element is at least one selected from the group consisting of magnesium, calcium, strontium and barium; in particular magnesium.
10. The method for producing 1-butene through isomerization according to claim 1, wherein the reaction temperature of the first reaction zone is 150-280 ℃, the reaction pressure is 0-1 MPa, and the weight space velocity is 1-10 hours-1(ii) a The preferable reaction temperature is 180-270 ℃, the pressure is 0.5-1 MPa, and the weight space velocity is 2-5 hours-1。
11. The method for producing 1-butene through isomerization according to claim 1, wherein the reaction temperature of the second reaction zone is 280-420 ℃, the pressure is 0-1 MPa, and the weight space velocity is 1-10 hours-1(ii) a The preferable contact temperature is 300-400 ℃, the pressure is 0.5-1 MPa, and the weight space velocity is 2-5 hours-1。
12. The isomerization process for producing 1-butene according to claim 1 wherein the reaction temperature in the first reaction zone is lower than the reaction temperature in the second reaction zone.
13. The method for producing 1-butene through isomerization according to claim 1, wherein the stream containing 2-butene is derived from a refinery catalytic cracking unit, an ethylene plant steam cracking unit or a coal-to-olefins unit by-product mixed carbon four stream, preferably a refinery catalytic cracking unit, an ethylene plant steam cracking unit or a coal-to-olefins unit by-product mixed carbon four stream with 1, 3-butadiene and isobutene removed.
14. Process for the isomerisation of 1-butene according to claim 1 characterised in that said stream containing 2-butene is a mixture containing 1-butene and 2-butene not complying with thermodynamic equilibrium values.
15. Process for the isomerisation of 1-butene according to claim 1 characterised in that said 2-butene containing stream has a mass concentration of 1-butene lower than 4% and a mass concentration of 2-butene higher than 45%.
16. Process for the isomerisation of 1-butene according to claim 1, characterised in that the mass concentration of 1, 3-butadiene in said stream containing 2-butene is lower than 30 ppm.
17. The method for producing 1-butene through isomerization according to claim 1, wherein the weight ratio of the catalyst A to the catalyst B is 0.1-8: 1, preferably 0.2-5: 1, and more preferably 0.5-4: 1.
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