CN111018650B - Butene isomerization process - Google Patents

Butene isomerization process Download PDF

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Publication number
CN111018650B
CN111018650B CN201811175357.8A CN201811175357A CN111018650B CN 111018650 B CN111018650 B CN 111018650B CN 201811175357 A CN201811175357 A CN 201811175357A CN 111018650 B CN111018650 B CN 111018650B
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butene
catalyst
zsm
isomerization process
molecular sieve
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CN111018650A (en
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龚海燕
刘俊涛
王誉蓉
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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
    • C07C5/27—Rearrangement of carbon atoms in the hydrocarbon skeleton
    • C07C5/2767—Changing the number of side-chains
    • C07C5/277—Catalytic processes
    • C07C5/2775—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
    • 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
    • B01J29/80—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
    • 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

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

Abstract

The application relates to a butene isomerization method. The method comprises the following steps: a) Feeding a feed stream containing 2-butene into a first reaction zone and contacting with a catalyst a to produce a stream I; b) Passing said stream I into at least one second reaction zone for contact with catalyst B to produce a 1-butene-containing product stream; wherein the catalyst A contains a molecular sieve Zr-ZSM with framework zirconium; the catalyst B contains silicon oxide or magnesium oxide.

Description

Butene isomerization process
Technical Field
The application relates to a butene isomerization method.
Background
1-butene is a relatively active alpha-olefin, and is mainly used for producing Linear Low Density Polyethylene (LLDPE), high Density Polyethylene (HDPE), polybutene (PB) resin, decanol and the like, and has very wide application. In recent years, the demand for polyethylene has grown rapidly worldwide, so that the demand for 1-butene as a comonomer has increased. However, most of domestic 1-butene manufacturers are self-use and sell the 1-butene from the outside in a small number, so that the 1-butene purchasing is difficult, and particularly enterprises with large gaps on the 1-butene are difficult.
At present, the global production of 1-butene mainly has two routes, one is oligomerization technology using ethylene as raw material, and the other is refinery C 4 Cleavage C 4 Or the byproduct mixture C of olefins produced by coal 4 Is obtained by separating the raw materials. The latter is commonly used in China, for mixing C 4 Butadiene extraction and hydrogenation are carried out, isobutene is removed through etherification, and then 1-butene product is obtained through rectification and separation. However, the yield of 1-butene in this route is limited by the source of 1-butene in the feedstock. Most petrochemical companies worldwide will be rich in 2-butene remaining C 4 Hydrocarbons are used as fuel. If the 2-butene is converted into 1-butene through isomerization reaction, a new way for producing 1-butene can be opened up.
In recent years, a great deal of research and development has been conducted on the process for producing 1-butene by isomerizing 2-butene by the relevant petrochemical companies at home and abroad. As disclosed in CN102267853A, a process for producing 1-butene by isomerizing 2-buteneThe method adopts the surface area of 150-210 m 2 Alumina per gram is taken as a carrier, 0.146 to 23.82 weight parts of metal salt is dissolved in 82 to 100 weight parts of deionized water to prepare aqueous solution, and then 57 weight parts of catalyst carrier is immersed; standing and soaking for 16-24 hours at room temperature, filtering residual liquid, drying for 4-10 hours at 120-160 ℃ until water is completely removed, and then roasting for 1-12 hours at 500-600 ℃ to obtain the metal composite oxide catalyst. The catalyst prepared by the method is filled in a fixed bed catalytic reactor, 2-butene gas with the content of 85.0 to 99.0 percent passes through the catalyst bed layer, the temperature is 300 to 480 ℃, the pressure is 0.1 to 0.5mpa, and the gas hourly space velocity of 2-butene feeding is 60 to 900 hours -1 Under the condition of (2) double bond isomerization reaction. And (3) carrying out gas timing sampling analysis after the reaction, wherein the content of 1-butene is 19.0-27.0%. When the reaction temperature is controlled to be lower (300-320 ℃), the content of the impurity isobutene generated by the reaction is lower, the 1-butene selectivity is higher, but the conversion rate is only 19%. When the reaction temperature is increased and the conversion rate is increased, the content of the impurity isobutene in the product is obviously increased, and particularly when the conversion rate reaches 24%, the isobutene content reaches 0.5%, and the selectivity of 1-butene is obviously reduced.
Since the isomerization of 2-butene to 1-butene is accompanied by other side reactions such as skeletal isomerization, dehydration and cracking in addition to the double bond isomerization of butene, these side reactions affect the selectivity of the reaction to 1-butene. Although the isomerization reaction can be carried out by a single kind of catalyst under a wide range of conditions, the conversion rate and the selectivity often cannot be considered when the reaction conditions are changed relatively widely.
Disclosure of Invention
The present inventors have made diligent studies on the basis of the prior art, and have completed the present application by solving at least one of the aforementioned problems by adopting a technical scheme of partition-loading catalysts of different catalytic activities.
In particular, the application relates to a butene isomerization process. The method comprises the following steps:
a) Feeding a feed stream containing 2-butene into a first reaction zone and contacting with a catalyst a to produce a stream I;
b) Passing said stream I into at least one second reaction zone for contact with catalyst B to produce a 1-butene-containing product stream;
wherein the catalyst A contains a molecular sieve Zr-ZSM with framework zirconium; the catalyst B contains silicon oxide or magnesium oxide.
According to one aspect of the present application, the catalyst A comprises, in parts by weight, 30 to 90 parts of Zr-ZSM and 10 to 70 parts of binder, preferably 40 to 80 parts of Zr-ZSM and 20 to 60 parts of binder, more preferably 50 to 80 parts of Zr-ZSM and 20 to 50 parts of binder; parts relative to the total weight of the Zr-ZSM and the binder.
According to one aspect of the present application, the Zr-ZSM molecular sieve is one of the group consisting of Zr-ZSM-5, zr-ZSM-11, zr-ZSM-35 and Zr-ZSM-39; preferably 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; more preferably at least two eutectic molecular sieves selected from the group consisting of Zr-ZSM-5, zr-ZSM-11, zr-ZSM-35 and Zr-ZSM-39; most preferred are Zr-ZSM-5/ZSM-11 eutectic molecular sieves.
According to an aspect of the present application, the binder is at least one selected from the group consisting of alumina and silica.
According to one aspect of the application, the Zr-ZSM molecular sieve has a molar ratio of Si to Zr of 50 to 1000, preferably 100 to 500.
According to one aspect of the application, the catalyst a does not contain alkaline earth metal elements or oxides thereof.
According to an aspect of the present application, 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 application, the reaction temperature of the first reaction zone is 150-280 ℃, the reaction pressure is 0-1 MPa, and the weight space velocity is 1-20 hours -1 The method comprises the steps of carrying out a first treatment on the surface of the Preferably, the reaction temperature is 180-270 ℃, the pressure is 0.5-1 MPa, and the weight airspeed is 2-10 hours -1 。
One according to the applicationThe reaction temperature of the second reaction zone is 280-420 ℃, the pressure is 0-1 MPa, and the weight airspeed is 1-20 hours -1 The method comprises the steps of carrying out a first treatment on the surface of the Preferably, the contact temperature is 320-400 ℃, the pressure is 0.5-1 MPa, and the weight airspeed is 2-10 hours -1 。
According to one aspect of the application, 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 application, the 2-butene-containing stream is derived from a refinery catalytic cracker, ethylene plant steam cracker or coal to olefin plant by-product mixed carbon four stream, preferably from a refinery catalytic cracker, ethylene plant steam cracker or coal to olefin plant by-product mixed carbon four stream after removal of 1, 3-butadiene, isobutylene.
According to one aspect of the application, the 2-butene-containing stream is a mixture containing 1-butene and 2-butene that does not meet thermodynamic equilibrium values.
According to one aspect of the application, 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%.
According to one aspect of the application, the mass concentration of 1, 3-butadiene in the 2-butene-containing stream is less than 30ppm.
According to one aspect of the application, the weight ratio of catalyst A to catalyst B is from 0.1 to 8:1, preferably from 0.2 to 5:1, more preferably from 0.5 to 4:1.
The application has the beneficial effects that:
according to the present application, the conversion of 2-butene and the selectivity of 1-butene can be simultaneously improved.
The application is further described by the following detailed description.
Detailed Description
The following describes specific embodiments of the present application in detail. It is to be noted that the scope of the application is not limited thereto but is defined by the appended claims.
All publications, patent applications, patents, and other references mentioned in this specification are incorporated herein by reference in their entirety. Unless defined otherwise, all technical and scientific terms used herein have the meaning commonly understood by one of ordinary skill in the art. In case of conflict, the present specification, definitions, will control.
When the specification derives materials, substances, methods, steps, devices, or elements and the like in the word "known to those skilled in the art", "prior art", or the like, such derived objects encompass those conventionally used in the art as the application suggests, but also include those which are not currently commonly used but which would become known in the art to be suitable for similar purposes.
In the context of this specification, any matters or matters not mentioned are directly applicable to those known in the art without modification except as explicitly stated. Moreover, any embodiment described herein can be freely combined with one or more other embodiments described herein, and the technical solutions or ideas thus formed are all deemed to be part of the original disclosure or original description of the present application, and should not be deemed to be a new matter which has not been disclosed or contemplated herein, unless such combination is clearly unreasonable by those skilled in the art.
Unless explicitly indicated, all percentages, parts, ratios, etc. mentioned in this specification are by weight unless otherwise clear to the routine knowledge of a person skilled in the art.
Unless explicitly indicated, all references to pressure in this specification refer to gauge pressure.
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein. In the following, the individual technical solutions can in principle be combined with one another to give new technical solutions, which should also be regarded as specifically disclosed herein.
It should be noted that, the double-bond isomerization reaction of 2-butene to 1-butene is a typical reversible reaction, and in general, the distribution of butene isomerization products is mainly controlled by thermodynamic factors. Therefore, different thermodynamic equilibrium conversions will correspond at different temperatures. Thermodynamic equilibrium conversion the reaction process can be thermodynamically calculated by means of the minimum gibbs free energy principle, as is well known to those skilled in the art.
The application relates to a butene isomerization method. The method comprises the following steps:
a) Feeding a feed stream containing 2-butene into a first reaction zone and contacting with a catalyst a to produce a stream I;
b) Passing said stream I into at least one second reaction zone for contact with catalyst B to produce a 1-butene-containing product stream;
wherein the catalyst A contains a molecular sieve Zr-ZSM with framework zirconium; the catalyst B contains silicon oxide or magnesium oxide.
According to the application, the catalyst A comprises 30 to 90 parts by weight of Zr-ZSM and 10 to 70 parts by weight of a first binder, preferably 40 to 80 parts by weight of Zr-ZSM and 20 to 60 parts by weight of a first binder, more preferably 50 to 80 parts by weight of Zr-ZSM and 20 to 50 parts by weight of a first binder; parts relative to the total weight of the Zr-ZSM and the first binder.
According to the present application, in the Zr-ZSM molecular sieve, the molar ratio of silicon to aluminum is 50 to 500, preferably 100 to 450, more preferably 200 to 400; the molar ratio of silicon to zirconium is 50-1000, preferably 100-500.
According to the present application, 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; it may also be 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 a 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 a Zr-ZSM-5/ZSM-11 eutectic molecular sieve. The eutectic molecular sieves described herein, which may also be referred to in the art as intergrowth molecular sieves, are distinguished from simple mechanical mixtures, but rather are two or more distinct phase intergrowth materials having a crystal structure in one molecular sieve composition.
According to the present application, the binder is at least one selected from the group consisting of alumina and silica.
According to one embodiment of the present application, the catalyst a does not contain an alkaline earth metal element or an oxide thereof from the viewpoint of more facilitating the 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 present application, the catalyst a may be prepared by the following method. The method comprises the following steps: crystallizing a mixture (hereinafter collectively referred to as a first mixture) containing a template agent, a zirconium source, a silicon source, an aluminum source, and water to obtain a Zr-ZSM molecular sieve, and molding the Zr-ZSM molecular sieve with a first binder.
Wherein the template agent is at least one selected from the group consisting of tetrapropylammonium hydroxide, tetrapropylammonium bromide, n-butylamine, tetramethyl ethylenediamine, cyclohexylamine, n-propylamine and hexamethylenetetramine.
The zirconium source may be any zirconium source conventionally used for this purpose in the art, including but not limited to zirconium nitrate, zirconium oxychloride and zirconium isopropoxide, preferably zirconium nitrate and zirconium oxychloride.
The silicon source may be any silicon source conventionally used for this purpose in the art. Examples include sodium silicate, silica sol and silicate ester. These silicon sources may be used singly or in combination of plural kinds in a desired ratio.
The aluminum source may be any aluminum source conventionally used in the art for this purpose. Examples thereof include aluminum sol and aluminum hydroxide. These aluminum sources may be used singly or in combination of plural kinds in a desired ratio.
In the first mixture, the templating agent, the zirconium source (in ZrO 2 Meter), the silicon source (in SiO 2 Meter), aluminum source (in Al 2 O 3 Calculated as a mole ratio of) and water is: 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 first mixture is controlled to have a ph=4 to 9, for which purpose any acid or base conventionally used in the art for this purpose can be used, for example hydrochloric acid, nitric acid, sulfuric acid, naOH, KOH and ammonia.
The crystallization may be performed in any manner conventionally known in the art, and for example, a method of subjecting the mixture to hydrothermal crystallization under crystallization conditions may be mentioned. Crystallization may be in the presence of agitation as desired. The crystallization conditions include: the temperature is 120-200 ℃ and the time is 20-80 hours.
Preferably, the method comprises an aging step performed before crystallization, and the aging conditions comprise: aging temperature is 30-75 ℃ and aging time is 10-48 hours.
After the crystallization is completed, the Zr-ZSM molecular sieve can be separated from the obtained reaction mixture by any conventionally known separation means. Examples of the separation method include 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 suction-filtered. The washing may be performed using deionized water and/or ethanol, for example. 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 performed under normal pressure or under reduced pressure.
The Zr-ZSM molecular sieve obtained by crystallization may be calcined as needed to remove the organic template agent, moisture which may be present, and the like, thereby obtaining a calcined molecular sieve. The calcination may be carried out in any manner conventionally known in the art, such as a calcination temperature of generally 300 to 800 ℃, preferably 400 to 650 ℃, and a calcination time of generally 1 to 10 hours, preferably 3 to 6 hours. In addition, the calcination is typically performed under an oxygen-containing atmosphere, such as air or an oxygen atmosphere.
And mixing the Zr-ZSM molecular sieve and the binder, and molding to obtain the catalyst A. The catalyst a may take the form of any molded article (such as a bar, a clover, etc.), and may be obtained in any manner conventionally known in the art, without particular limitation. The first binder may be any binder conventionally used for this purpose in the art. Examples thereof include alumina and silica. Preferably, a porogen may be added during the molding process. The porogen may be any porogen conventionally used in the art for this purpose. For example, sesbania powder and methylcellulose may be mentioned.
The molded catalyst a may be dried and calcined as needed. The drying may be performed 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 performed under normal pressure or under reduced pressure. The calcination may be carried out in any manner conventionally known in the art, such as a calcination temperature of generally 300 to 800 ℃, preferably 400 to 650 ℃, and a calcination time of generally 1 to 10 hours, preferably 3 to 6 hours. In addition, the calcination is typically performed under an oxygen-containing atmosphere, such as air or an oxygen atmosphere.
In the method for producing the catalyst a, the first mixture does not contain an alkaline earth metal source from the viewpoint of more facilitating the isomerization reaction. The alkaline earth metal is at least one selected from the group consisting of magnesium, calcium, strontium and barium; in particular magnesium. Here, the term "not including an alkaline earth metal source" means that the alkaline earth metal source is not intentionally or actively introduced during the preparation process.
According to the application, the catalyst A contains Zr-ZSM with framework zirconium. The skeleton Zr can improve the acidity of the molecular sieve, and ensures that the catalyst A has higher activity. Depending on this property of catalyst a, the first reaction zone is controlled at a lower reaction temperature. The reaction conditions of the first reaction zone include: the reaction temperature is 150-280 ℃, and the reaction is carried outThe stress is 0-1 MPa, and the weight airspeed is 1-20 hours -1 The method comprises the steps of carrying out a first treatment on the surface of the Preferably, the reaction temperature is 180-270 ℃, the pressure is 0.5-1 MPa, and the weight airspeed is 2-10 hours -1 。
According to the application, the catalyst B contains silicon oxide or magnesium oxide. Silica or magnesia are well known in the art as butene isomerization catalysts, for example documents US6875901, CN102649672a. The reaction conditions of the second reaction zone include: the reaction temperature is 280-420 ℃, the pressure is 0-1 MPa, and the weight airspeed is 1-20 hours -1 The method comprises the steps of carrying out a first treatment on the surface of the Preferably, the contact temperature is 320-400 ℃, the pressure is 0.5-1 MPa, and the weight airspeed is 2-10 hours -1 。
According to the application, the weight ratio of catalyst A to catalyst B is from 0.1 to 8:1, preferably from 0.2 to 5:1, more preferably from 0.5 to 4:1.
According to the application, molecular sieve Zr-ZSM with skeleton zirconium is adopted in the first reaction zone, the conversion degree of 2-butene in the first reaction zone is higher, the amount of 2-butene which is involved in the reaction in the second reaction zone is smaller, so that the reaction intensity in the second reaction zone is lower, and the effects of high conversion rate and high selectivity are achieved finally.
In the present application, 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 conditions: an iCAP7600Duo inductively coupled plasma emission spectrometer of Siemens Feier company of the United states is adopted, zirconia is adopted as a standard sample, and the RF power of the instrument is 1.2KW; carrier gas flow rate is 0.72L/min; the cooling air flow is 15L/min; the pump flow rate was 1.0ml/min and the analysis wavelength was 335nm. XRF was used to test the molecular sieve content in the catalyst under the following conditions: the 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 120mA.
The crystalline phase of the catalyst A in the application is carried out on a Bruker D8 type polycrystalline X-ray diffraction (XRD) instrument, and a Cu-Ka ray source (K alpha 1 wavelength lambda= 0.15406 nm) is used for the graphite monochromator, wherein the scanning angle 2 theta is 5-50 degrees, and the scanning speed is 1 degree/min.
The Zr existing form in the catalyst A is measured by a Cary5000 ultraviolet visible spectrum (UV-vis) instrument, solid barium sulfate is used as a reference, and the test wavelength range is 190-800. The multi-coordinated zirconium in the molecular sieve framework can generate absorption peaks at the wavelength of 240-280 nm, and the absorption peak of the zirconia is smaller than 200nm.
In the application, the product composition is measured by a gas chromatography, the chromatography model is Agilent 7890A, a FID detector is arranged, the FFAP capillary chromatographic column is used for separation, the chromatographic column is heated by a program, the initial temperature is 90 ℃, the temperature is kept for 15 minutes, and then the temperature is raised to 220 ℃ at the speed of 15 ℃/minute, and the temperature is kept for 45 minutes.
The conversion rate X of the 2-butene is calculated as follows:
X( 2-butene )＝(M Inlet 2-butene -M Outlet 2-butene )/M Inlet 2-butene ×100％
The selectivity Y of the 1-butene is calculated as follows:
Y( 1-butene )＝M( Outlet 1-butene )/(M Inlet 2-butene -M Outlet 2-butene )×100％
The application is further illustrated by the following examples.
[ example 1 ]
1) 6g of zirconium oxychloride was dissolved in isopropanol, and then added to 1000ml of ethyl orthosilicate to prepare a mixed solution I, and stirred at room temperature for 50 minutes. 2700ml of an aqueous solution containing 10% tetrapropylammonium hydroxide was prepared to prepare solution II. 30g of alumina sol (40% alumina content) 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 regulating the pH value to be=6 by using nitric acid and ammonia water to obtain feed liquid IV; after being stirred uniformly, the feed liquid IV is placed in a crystallization kettle to be aged for 20 hours at 45 ℃ and crystallized for 48 hours at 170 ℃; and taking out the material after crystallization, carrying out vacuum filtration, washing with deionized water, drying in an oven at 120 ℃, and roasting at 550 ℃ for 4 hours to obtain the molecular sieve powder Z1-a. 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.
Taking 70g of the Z1-a molecular sieve, 30g of alumina, 60ml of 0.5% nitric acid and 5g of sesbania powder, kneading, extruding, baking at 120 ℃ for 4 hours, baking at 500 ℃ for 4 hours, and loading into a first reactor to obtain a catalyst A1.
2) Mixing 100g of magnesium oxide and 0.5g of methyl cellulose, tabletting and molding, treating the molded catalyst with 200ml of 0.2% citric acid for 3 hours, washing with deionized water, drying at 120 ℃ and roasting at 500 ℃ to obtain a catalyst B1, and loading the catalyst B1 into a second reactor.
The results of the catalyst analysis test are shown in Table 1.
[ example 2 ]
1) 70g of Z1-a molecular sieve, 75ml of silica sol (containing 40% SiO) 2 ) Kneading with 5g sesbania powder, extruding, baking at 120deg.C for 4 hr, and baking at 500deg.C for 4 hr to obtain catalyst A2, and loading into the first reactor.
2) B1 catalyst prepared as described in example 1 was charged to the second reaction zone.
The analytical test results are shown in Table 1.
[ example 3 ]
1) 50g of Z1-a molecular sieve, 50g of alumina, 60ml of 0.5% nitric acid and 5g of sesbania powder are taken, kneaded and extruded, baked for 4 hours at 120 ℃ and baked for 4 hours at 500 ℃ to obtain a catalyst A3, and the catalyst A3 is filled into a first reactor.
2) B1 catalyst prepared as described in example 1 was charged to the second reaction zone.
The analytical test results are shown in Table 1.
[ example 4 ]
1) 42g of Z1-a molecular sieve, 58g of alumina, 60ml of 0.5% nitric acid and 5g of sesbania powder are taken, kneaded and extruded, baked for 4 hours at 120 ℃ and baked for 4 hours at 500 ℃ to obtain a catalyst A4, and the catalyst A4 is filled into a first reactor.
2) B1 catalyst prepared as described in example 1 was charged to the second reaction zone.
The analytical test results are shown in Table 1.
[ example 5 ]
1) 31g of Z1-a molecular sieve, 69g of alumina, 60ml of 0.5% nitric acid and 5g of sesbania powder are taken for kneading and extruding, the mixture is baked for 4 hours at 120 ℃ and then baked for 4 hours at 500 ℃, and then the catalyst A5 is obtained and is filled into a first reactor.
2) B1 catalyst prepared as described in example 1 was charged to the second reaction zone.
The analytical test results are shown in Table 1.
[ example 6 ]
1) Taking 85g of Z1-a molecular sieve, 15g of alumina, 60ml of 0.5% nitric acid and 5g of sesbania powder, kneading and extruding, baking at 120 ℃ for 4 hours, and baking at 500 ℃ for 4 hours to obtain a catalyst A6, and loading the catalyst A6 into a first reactor.
2) B1 catalyst prepared as described in example 1 was charged to the second reaction zone.
The analytical test results are shown in Table 1.
[ example 7 ]
1) 1g of zirconium oxychloride was dissolved in isopropanol, and then added to 1000ml of ethyl orthosilicate to prepare a mixed solution I, and stirred at room temperature for 50 minutes. 2700ml of an aqueous solution containing 10% tetrapropylammonium hydroxide was prepared to prepare solution II. 30g of alumina sol (40% alumina content) 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 regulating the pH value to be=6 by using nitric acid and ammonia water to obtain feed liquid IV; after being stirred uniformly, the feed liquid IV is placed in a crystallization kettle to be aged for 20 hours at 45 ℃ and crystallized for 48 hours at 170 ℃; and taking out the material after crystallization, carrying out vacuum filtration, washing with deionized water, drying in an oven at 120 ℃, and roasting at 550 ℃ for 4 hours to obtain the molecular sieve powder Z7-a. 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.
Taking 70g of the Z7-a molecular sieve, 30g of alumina, 60ml of 0.5% nitric acid and 5g of sesbania powder, kneading, extruding, baking at 120 ℃ for 4 hours, baking at 500 ℃ for 4 hours, and loading into a first reactor to obtain a catalyst A7.
2) B1 catalyst prepared as described in example 1 was charged to the second reaction zone.
The analytical test results are shown in Table 1.
[ example 8 ]
1) 4g of zirconium oxychloride was dissolved in isopropanol, and then added to 1000ml of ethyl orthosilicate to prepare a mixed solution I, and stirred at room temperature for 50 minutes. 2700ml of an aqueous solution containing 10% tetrapropylammonium hydroxide was prepared to prepare solution II. 30g of alumina sol (40% alumina content) 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 regulating the pH value to be=6 by using nitric acid and ammonia water to obtain feed liquid IV; after being stirred uniformly, the feed liquid IV is placed in a crystallization kettle to be aged for 20 hours at 45 ℃ and crystallized for 48 hours at 170 ℃; and taking out the material after crystallization, carrying out vacuum filtration, washing with deionized water, drying in an oven at 120 ℃, and roasting at 550 ℃ for 4 hours to obtain the molecular sieve powder Z8-a. 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.
Taking 70g of the Z8-a molecular sieve, 30g of alumina, 60ml of 0.5% nitric acid and 5g of sesbania powder, kneading, extruding, baking at 120 ℃ for 4 hours, baking at 500 ℃ for 4 hours, and loading into a first reactor to obtain a catalyst A8.
2) B1 catalyst prepared as described in example 1 was charged to the second reaction zone.
The analytical test results are shown in Table 1.
[ example 9 ]
1) 23g of zirconium oxychloride was dissolved in isopropanol, and then added to 1000ml of ethyl orthosilicate to prepare a mixed solution I, and stirred at room temperature for 50 minutes. 2700ml of an aqueous solution containing 10% tetrapropylammonium hydroxide was prepared to prepare solution II. 30g of alumina sol (40% alumina content) 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 regulating the pH value to be=6 by using nitric acid and ammonia water to obtain feed liquid IV; after being stirred uniformly, the feed liquid IV is placed in a crystallization kettle to be aged for 20 hours at 45 ℃ and crystallized for 48 hours at 170 ℃; and taking out the material after crystallization, carrying out vacuum filtration, washing with deionized water, drying in an oven at 120 ℃, and roasting at 550 ℃ for 4 hours to obtain the molecular sieve powder Z9-a. 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.
Taking 70g of the Z9-a molecular sieve, 30g of alumina, 60ml of 0.5% nitric acid and 5g of sesbania powder, kneading, extruding, baking at 120 ℃ for 4 hours, baking at 500 ℃ for 4 hours, and loading into a first reactor to obtain a catalyst A9.
2) B1 catalyst prepared as described in example 1 was charged to the second reaction zone.
The analytical test results are shown in Table 1.
[ example 10 ]
1) The A8 catalyst prepared [ example 8 ] was charged to the first reactor.
2) 100g of silicon oxide (specific surface more than 400 m) 2 Per gram, average pore diameter of 1.5-4 nm) and 0.5g of methyl cellulose, tabletting, drying at 120 ℃ and roasting at 500 ℃, and loading the obtained catalyst B10 into a second reactor.
The analytical test results are shown in Table 1.
[ example 11 ]
1) 6g of zirconium oxychloride was dissolved in isopropanol, and then added to 1000ml of ethyl orthosilicate to prepare a mixed solution I, and stirred at room temperature for 50 minutes. 2700ml of an aqueous solution containing 10% tetrapropylammonium hydroxide was prepared to prepare solution II. 30g of alumina sol (40% alumina content) 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 regulating the pH value to be=6 by using nitric acid and ammonia water to obtain feed liquid IV; after being stirred uniformly, the feed liquid IV is placed in a crystallization kettle to be aged for 20 hours at 45 ℃ and crystallized for 48 hours at 170 ℃; and taking out the material after crystallization, carrying out vacuum filtration, washing with deionized water, drying in an oven at 120 ℃, and roasting at 550 ℃ for 4 hours to obtain the 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 containing framework zirconium.
Taking 70g, 30g of alumina, 1g of magnesia, 60ml of 0.5% nitric acid and 5g of sesbania powder of the Z11-a molecular sieve, kneading, extruding, baking at 120 ℃ for 4 hours, and baking at 500 ℃ for 4 hours to obtain the catalyst A11.
2) B1 catalyst prepared as described in example 1 was charged to the second reaction zone.
The analytical test results are shown in Table 1.
[ example 12 ]
1) 6g of zirconium oxychloride was dissolved in isopropanol, and then added to 700ml of silica sol (40% SiO 2) to prepare a mixed solution I, and stirred at room temperature for 50 minutes. 2700ml of an aqueous solution containing 8% n-butylamine was prepared to prepare solution II. 10g of aluminum hydroxide is added into the solution II under stirring to obtain a feed liquid III. Slowly adding the solution I into the feed liquid III under the stirring state, and regulating the pH value to be=6 by using nitric acid and ammonia water to obtain feed liquid IV; after being stirred uniformly, the feed liquid IV is placed in a crystallization kettle to be aged for 20 hours at 45 ℃ and crystallized for 50 hours at 165 ℃; and taking out the material after crystallization, carrying out vacuum filtration, washing with deionized water, drying in an oven at 120 ℃, and roasting at 550 ℃ for 4 hours to obtain the molecular sieve powder Z12a-1. The obtained molecular sieve is characterized by XRD and UV-vis, and the crystal form is ZSM-5 molecular sieve containing framework zirconium.
6g of zirconium oxychloride was dissolved in isopropanol, and then added to 700ml of silica sol (40% SiO 2) to prepare a mixed 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 is added into the solution II under stirring to obtain a feed liquid III. Slowly adding the solution I into the feed liquid III under the stirring state, and regulating pH=4 by using nitric acid and ammonia water to obtain feed liquid IV; after being stirred uniformly, the feed liquid IV is placed in a crystallization kettle for aging for 20 hours at 45 ℃ and then crystallized for 48 hours at 135 ℃; and taking out the material after crystallization, carrying out vacuum filtration, washing with deionized water, drying in an oven at 120 ℃, and roasting at 550 ℃ for 4 hours to obtain the molecular sieve powder Z12a-2. The obtained molecular sieve is characterized by XRD and UV-vis, and the crystal form is ZSM-11 molecular sieve containing framework zirconium.
Kneading 35g of each of the molecular sieves Z12a-1 and Z12a-2, 30g of alumina, 60ml of 0.5% nitric acid and 5g of sesbania powder, extruding, baking at 120 ℃ for 4 hours, baking at 500 ℃ for 4 hours, and loading the catalyst A12 into a first reactor.
2) B1 catalyst prepared as described in example 1 was charged to the second reaction zone.
The analytical test results are shown in Table 1.
[ example 13 ]
1) 6g of zirconium oxychloride was dissolved in isopropanol, and then added to 1000ml of ethyl orthosilicate to prepare a mixed solution I, and stirred at room temperature for 50 minutes. 2700ml of an aqueous solution containing 11% of tetramethyl ethylenediamine was prepared to prepare a solution II. 50g of aluminum sulfate is added into the solution II under stirring to obtain a feed liquid III. Slowly adding the solution I into the feed liquid III under the stirring state, and regulating the pH value to be=6 by using nitric acid and ammonia water to obtain feed liquid IV; after being stirred uniformly, the feed liquid IV is placed in a crystallization kettle for aging for 20 hours at 45 ℃ and then crystallized for 48 hours at 180 ℃; and taking out the material after crystallization, carrying out vacuum filtration, washing with deionized water, drying in an oven at 120 ℃, and roasting at 550 ℃ for 4 hours to obtain the molecular sieve powder Z13-a. 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.
Taking 70g of the Z13-a molecular sieve, 30g of alumina, 60ml of 0.5% nitric acid and 5g of sesbania powder, kneading, extruding, baking at 120 ℃ for 4 hours, baking at 500 ℃ for 4 hours, obtaining a catalyst A13, and loading into a first reactor.
2) B1 catalyst prepared as described in example 1 was charged to the second reaction zone.
The analytical test results are shown in Table 1.
[ example 14 ]
1) A Zr-ZSM-5 molecular sieve Z12a-1 was prepared in the same manner as in example 12, 70g of the above-mentioned Z12a-1 molecular sieve, 30g of alumina, 60ml of 0.5% nitric acid and 5g of sesbania powder were kneaded and extruded into strips, baked at 120℃for 4 hours and then baked at 500℃for 4 hours to obtain a catalyst A14, which was charged into the first reactor.
2) B1 catalyst prepared as described in example 1 was charged to the second reaction zone.
The analytical test results are shown in Table 1.
[ example 15 ]
1) Zr-ZSM-11 molecular sieve Z12a-2 was prepared in the same manner as in example 12, 70g, 30g of alumina, 60ml of 0.5% nitric acid and 5g of sesbania powder were kneaded and extruded, baked at 120℃for 4 hours and baked at 500℃for 4 hours to obtain catalyst A15, which was then fed into the first reactor.
2) B1 catalyst prepared as described in example 1 was charged to the second reaction zone.
The analytical test results are shown in Table 1.
[ example 16 ]
1) 6g of zirconium oxychloride was dissolved in isopropanol, and then added to 700ml (40% SiO 2) to prepare a mixed solution I, and stirred at room temperature for 50 minutes. 2700ml of an aqueous solution containing 11% cyclohexylamine was prepared to prepare a solution II. 40g of aluminum sulfate was added to the solution II under stirring to obtain a feed liquid III. Slowly adding the solution I into the feed liquid III under the stirring state, and regulating the pH value to be=6 by using nitric acid and ammonia water to obtain feed liquid IV; after being stirred uniformly, the feed liquid IV is placed in a crystallization kettle for aging for 20 hours at 45 ℃ and then crystallized for 48 hours at 180 ℃; and taking out the material after crystallization, carrying out vacuum filtration, washing with deionized water, drying in an oven at 120 ℃, and roasting at 550 ℃ for 4 hours to obtain the molecular sieve powder Z16-a. The obtained molecular sieve is characterized by XRD and UV-vis, and the crystal form is ZSM-35 molecular sieve containing framework zirconium.
Taking 70g of the Z16-a 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 baking at 500 ℃ for 4 hours to obtain a catalyst A16, and loading the catalyst A16 into a first reactor.
2) B10 catalyst prepared as described in example 10 was charged to the second reaction zone.
The analytical test results are shown in Table 1.
[ example 17 ]
1) 6g of zirconium oxychloride was dissolved in isopropanol, and then added to 700ml (40% SiO 2) to prepare a mixed solution I, and stirred at room temperature for 50 minutes. 2700ml of an aqueous solution containing 4% of n-propylamine and 8% of hexamethylenetetramine (R2) was prepared to prepare a solution II. 5g of aluminum sulfate is added into the solution II under stirring to obtain a feed liquid III. Slowly adding the solution I into the feed liquid III under the stirring state, and regulating the pH value to be 4 by sulfuric acid to obtain a feed liquid IV; after being stirred uniformly, the feed liquid IV is placed in a crystallization kettle to be aged for 20 hours at 60 ℃, and then crystallized for 130 hours at 180 ℃; and taking out the material after crystallization, carrying out vacuum filtration, washing with deionized water, drying in an oven at 120 ℃, and roasting at 550 ℃ for 4 hours to obtain the molecular sieve powder Z17-a. The obtained molecular sieve is characterized by XRD and UV-vis, and the crystal form is ZSM-39 molecular sieve containing framework zirconium.
Taking 70g of the Z17-a molecular sieve, 30g of alumina, 60ml of 0.5% nitric acid and 5g of sesbania powder, kneading, extruding, baking at 120 ℃ for 4 hours, baking at 500 ℃ for 4 hours, and loading into a first reactor to obtain a catalyst A17.
2) B1 catalyst prepared as described in example 1 was charged to the second reaction zone.
The analytical test results are shown in Table 1.
[ comparative example 1 ]
Catalyst A1 was charged to the first and second reaction zones, respectively.
The analytical test results are shown in Table 1.
[ comparative example 2 ]
Catalyst B1 was charged into the first and second reaction zones, respectively.
The analytical test results are shown in Table 1.
Example 18
Examine the application of the two catalysts A/B in butene double bond isomerization reactions in examples 1-17.
Catalysts according to examples 1-17 of the present application were loaded into the first and second reaction zones, respectively, in the manner shown in Table 1 for reaction evaluation. The mixed C4 of the n-butane 12.1%, the cis-2-butene 35.6% and the trans-2-butene 51.3 is used as a raw material. The temperature of the reactor I is controlled to be 250 ℃, the reaction pressure is controlled to be 0.4MPa, and the weight space velocity is controlled to be 8 hours -1 The temperature of the reactor II is 350 ℃, the reaction pressure is 0.4MPa, and the weight space velocity is 8 hours -1 The catalyst was evaluated under the conditions, and the reaction results are shown in Table 2.
[ comparative example 3 ]
The first and second reaction zones were charged respectively in the manner shown in Table 1 of the catalyst [ comparative examples 1-2 ] for reaction evaluation. The mixed C4 of the n-butane 12.1%, the cis-2-butene 35.6% and the trans-2-butene 51.3 is used as a raw material. The temperature of the reactor I is controlled to be 250 ℃, the reaction pressure is controlled to be 0.4MPa, and the weight space velocity is controlled to be 8 hours -1 The temperature of the reactor II is 350 ℃, the reaction pressure is 0.4MPa, and the weight space velocity is 10 hours -1 The catalyst was evaluated under the conditions, and the reaction results are shown in Table 2.
TABLE 1
TABLE 2
Catalyst loading Conversion of 2-butene% N-butene selectivity,%
Example 1 22.27 99.21
Example 2 22.17 99.18
Example 3 22.27 99.10
Example 4 21.97 99.10
Example 5 21.77 99.00
Example 6 22.37 98.80
Example 7 21.87 99.10
Example 8 22.37 98.90
Example 9 22.37 98.70
Example 10 21.87 99.30
Example 11 19.86 99.20
Example 12 19.76 99.10
Example 13 21.97 99.00
Example 14 22.17 98.90
Example 15 22.37 98.80
Example 16 22.27 98.90
Example 17 22.37 99.00
Comparative example 1 22.1 93.76
Comparative example 2 16.33 97.68
Therefore, the catalyst with different activities is filled in the partitions, so that higher conversion rate and selectivity can be obtained at the same time, and the comprehensive performance is obviously higher than that of the comparative example.
Examples 19 to 25
Catalysts A1 and B1 obtained in the application [ example 1 ] were subjected to reaction evaluation in the manner of [ example 18 ], and the process conditions were changed to test, and the reaction conditions and the results are shown in Table 3.
TABLE 3 Table 3
[ comparative example 4 ]
The first reaction zone is SiO using the method disclosed in document CN102649671A 2 /Al 2 O 3 The ZSM-11 molecular sieve with the molar ratio of 200 and the second reaction zone is silicon oxide.
The mixed C4 of the n-butane 12.1%, the cis-2-butene 35.6% and the trans-2-butene 51.3 is used as a raw material. The temperature of the first reaction zone is controlled to 320 ℃, the reaction pressure is controlled to 0.8MPa, and the weight space velocity is controlled to 20 hours -1 The temperature of the second reaction zone is 340 ℃, the reaction pressure is 0.5MPa, and the weight space velocity is 10 hours -1 The 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%.
Comparative example 4 the catalyst employed in the first reaction zone was an unmodified ZSM-11 molecular sieve which was less acidic and less active than the molecular sieve Zr-ZSM having framework zirconium of the present application. Compared with the method of the comparative example 4, the conversion degree of the 2-butene in the first reaction zone is higher, the amount of the 2-butene which is involved in the reaction in the second reaction zone is smaller, so that the reaction severity of the second reaction zone is lower, and the final high conversion rate and high selectivity are ensured.

Claims (17)

1. A butene isomerization process comprising the steps of:
a) Feeding a feed stream containing 2-butene into a first reaction zone and contacting with a catalyst a to produce a stream I;
b) Passing said stream I into at least one second reaction zone for contact with catalyst B to produce a 1-butene-containing product stream;
wherein the catalyst A contains a molecular sieve Zr-ZSM with framework zirconium; the catalyst B contains silicon oxide or magnesium oxide;
the Zr-ZSM molecular sieve is a Zr-ZSM-5/ZSM-11 eutectic molecular sieve or a Zr-ZSM-5/ZSM-35 eutectic molecular sieve;
the catalyst A comprises 50-80 parts of Zr-ZSM and 20-50 parts of binder; parts by weight relative to total weight of the Zr-ZSM and the binder; in the Zr-ZSM molecular sieve, the molar ratio of silicon to zirconium is 100-500;
the catalyst a does not contain an alkaline earth metal element or an oxide thereof;
the reaction temperature of the first reaction zone is 150-280 ℃, the reaction pressure is 0-1 MPa, and the weight airspeed is 1-20 hours -1 。
2. The butene isomerization process of claim 1, wherein the Zr-ZSM molecular sieve is a Zr-ZSM-5/ZSM-11 eutectic molecular sieve.
3. The butene isomerization process of claim 1 wherein the binder is selected from at least one of the group consisting of alumina and silica.
4. The butene isomerization process of claim 1 wherein the alkaline earth metal element is selected from at least one of the group consisting of magnesium, calcium, strontium and barium.
5. The butene isomerization process according to claim 1, wherein the alkaline earth metal element is magnesium.
6. The butene isomerization process according to claim 1, wherein the first reaction zone has a reaction temperature of 180-270 ℃, a pressure of 0.5-1 MPa and a weight space velocity of 2-10 hours -1 。
7. The butene isomerization process according to claim 1 wherein the second reaction zone has a reaction temperature of 280-420 ℃, a pressure of 0-1 MPa and a weight space velocity of 1-20 hours -1 。
8. The butene isomerization process according to claim 1 wherein the second reaction zone has a reaction temperature of 320-400 ℃, a pressure of 0.5-1 MPa and a weight space velocity of 2-10 hours -1 。
9. The butene isomerization process of claim 1 wherein the reaction temperature of the first reaction zone is lower than the reaction temperature of the second reaction zone.
10. The butene isomerization process of claim 1 wherein the 2-butene containing stream is derived from a refinery catalytic cracker, ethylene plant steam cracker or coal-to-olefin plant by-product mixed carbon four stream.
11. The butene isomerization process of claim 1 wherein the 2-butene containing stream is derived from a refinery catalytic cracker, ethylene plant steam cracker or coal-to-olefin plant by-product mixed carbon four stream after removal of 1, 3-butadiene, isobutylene.
12. The butene isomerization process of claim 1 wherein the 2-butene containing stream is a mixture comprising 1-butene and 2-butene that does not meet thermodynamic equilibrium values.
13. The butene isomerization process of claim 1 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%.
14. The butene isomerization process of claim 1 wherein the mass concentration of 1, 3-butadiene in the 2-butene containing stream is less than 30ppm.
15. The butene isomerization process according to claim 1 wherein the weight ratio of catalyst a to catalyst B is from 0.1 to 8:1.
16. The butene isomerization process according to claim 1 wherein the weight ratio of catalyst a to catalyst B is from 0.2 to 5:1.
17. The butene isomerization process according to claim 1 wherein the weight ratio of catalyst a to catalyst B is from 0.5 to 4:1.
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CN105268475A (en) * 2014-07-24 2016-01-27 中国石油化工股份有限公司 Method for preparing isobutene through n-butene skeletal isomerization
CN105709841A (en) * 2016-01-18 2016-06-29 张玲 Preparation of n-butene skeletal isomerization catalyst

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CN1170632A (en) * 1996-07-15 1998-01-21 中国科学院大连化学物理研究所 Catalyst for isobutane preparing reaction by normal butane isomerization and its use
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
CN103379956A (en) * 2010-12-21 2013-10-30 巴斯夫公司 Isomerization catalysts
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