CN108636448A - A kind of catalyst for producing ethylene from dehydration of ethanol - Google Patents
A kind of catalyst for producing ethylene from dehydration of ethanol Download PDFInfo
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- CN108636448A CN108636448A CN201810348595.8A CN201810348595A CN108636448A CN 108636448 A CN108636448 A CN 108636448A CN 201810348595 A CN201810348595 A CN 201810348595A CN 108636448 A CN108636448 A CN 108636448A
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- 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
- B01J29/005—Mixtures of molecular sieves comprising at least one molecular sieve which is not an aluminosilicate zeolite, e.g. from groups B01J29/03 - B01J29/049 or B01J29/82 - B01J29/89
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- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
- C07C1/24—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms by elimination of water
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- 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
-
- 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
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- 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
- B01J29/82—Phosphates
- B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
- B01J29/85—Silicoaluminophosphates (SAPO compounds)
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/82—Phosphates
- C07C2529/84—Aluminophosphates containing other elements, e.g. metals, boron
- C07C2529/85—Silicoaluminophosphates (SAPO compounds)
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The present invention relates to a kind of catalyst for producing ethylene from dehydration of ethanol, using alkali metal and rare-earth metal modified HZSM-5/SAPO-11 molecular sieves, when catalysis ethanol is dehydrated ethylene method processed, ethanol conversion and ethylene selectivity reach 99.9% or more, and successive reaction 100h, ethanol conversion and ethylene selectivity are still maintained at 97%.
Description
Technical field
The technical field prepared the present invention relates to ethylene more particularly to a kind of catalyst for producing ethylene from dehydration of ethanol.
Background technology
The production scale and technical merit of ethylene are the important symbols of the chemical Industry Development Level of a country.With economy
Continuous development, oneself demand through demand and consumption big country, especially ethylene as the energy and resource of China is every in recent years
Year is all increased with average 20% speed, but the yield wretched insufficiency of ethylene, the domestic city of ethylene and downstream derivative
The Service Efficiency of field is average less than 50, needs a large amount of imports.The production method of ethylene mainly still uses naphtha both at home and abroad at present
Cracking process, but with the growing tension of the global energy and resource supply-demand relationship, which will be faced with formidable challenges.With life
Ethyl alcohol obtained by fermentation of materials is raw material, and the technique that ethylene is prepared through catalytic dehydration receives more and more attention.On the one hand, raw
Physical resources are derived from a wealth of sources, rich reserves, are regenerated every year；On the other hand, being constantly progressive with industrial biotechnology, second of fermenting
The production cost of alcohol constantly declines so that is accordingly declined by producing ethylene with ethyl alcohol production cost, therefore, by catalytic dehydration of ethanol second
Alkene is just showing increasing economic competition advantage relative to traditional petroleum path ethylene.
The molecular sieve catalyst for producing ethylene from dehydration of ethanol reported has：4A molecular sieves, SAPO-34 molecular sieves, H-
H-NaZSM-5, HY type molecular sieve, the H beta-molecular sieves of modenite, V-MCM-41, H-NaZSM-5 molecular sieve, different silica alumina ratios
Equal wherein ZSM-5 molecular sieve catalyst is more advantageous in catalytic dehydration aspect of performance due to lipophilic-hydrophobic property, therefore
Many researchers have carried out study on the modification to ZSM-5 molecular sieve.
Producing ethylene from dehydration of ethanol is an acid catalyzed reaction process, and catalyst surface acidity is stronger, the easier absorption of ethyl alcohol, production
Object ethylene difficulty is desorbed, and easily absorption on a catalyst, causes ethylene selectivity to decline, while will produce polymerisation and causing catalyst
Coking deactivation.If catalyst surface acid strength is weaker, reaction conversion ratio is relatively low.Thus in ethanol dehydration reaction, suitable acid
Amount and acid strength are conducive to ethylene product generation, and molecular sieve surface is acid too strong or excessively weak is all unfavorable for its reaction.H‐NZSM‐5
The stronger acid and limited aperture in surface makes product have very strong aromatisation trend, and side reaction is more in reaction, ethylene selectivity
It is low.And SAPO-34 molecular sieves then have smaller (the about 0.43nm, with ethanol molecule equivalent in aperture compared with H-ZSM-5 molecular sieves
Diameter is identical), the advantages that porosity is high, big using specific surface, and hydrothermal stability is preferable, this makes SAPO-34 molecular sieves exist
Preferable catalytic activity and selectivity are showed in producing ethylene from dehydration of ethanol reaction.However, simple SAPO-34 molecular sieves are used as
Catalytic efficiency is relatively low when catalyst for ethanol delydration to ethylene.Currently, molecular sieve modified to SAPO-34 mainly by various gold
Belong to element to introduce on SAPO-34 framework of molecular sieve, change acidic zeolite and aperture size, is conducive to improve ethylene selectivity,
Also one will be compounded in different ducts and acid two kinds of molecular sieves of H-NaZSM-5 and SAPO-34 by synthetic method by having
Rise, prepare it is acid it is moderate, sour be evenly distributed, the catalyst with good pore passage structure, but catalytic effect cannot still make us full
Meaning.
Invention content
To solve the above problems, the present invention will be mainly by that will have different ducts and acid H-NaZSM-5 and SAPO-
34 two kinds of molecular sieves are combined with each other the common modification by alkali metal and rare earth metal by synthetic method, prepare acidity
It is moderate, sour be evenly distributed, the catalyst with good pore passage structure, improve the catalytic activity and stabilization of producing ethylene from dehydration of ethanol
Property.
Specifically, the present invention provides a kind of catalyst for producing ethylene from dehydration of ethanol, it is characterised in that：Alkali metal and dilute
Earth metal modified HZSM-5/SAPO-11 composite molecular screens simultaneously, wherein alkali metal accounts for the 1%~2% of total catalyst weight, dilute
Earth metal accounts for the 3.5~4.8% of overall catalyst weight；The preparation method of the catalyst is as follows：By commercial HZSM-5 molecular sieves
It is mixed with deionized water, alkali metal source is added and slurries I is made in rare earth metal source；Distilled water, phosphorus source, silicon source, silicon source are pressed one
Fixed mol ratio is mixed, is stirred, and gel II is made；Slurries I is poured into gel II, stirs, adds dropwise by certain mol proportion
Enter template, stirring forms homogeneous gel；Gel is added in reaction kettle, crystallization takes out cooling after a certain period of time, filtration washing,
It dries, is obtained in Muffle kiln roasting removed template method at a certain temperature.
The preparation method of catalyst of the present invention is as follows：
The preparation method of the catalyst is as follows：Commercial HZSM-5 molecular sieves are mixed with deionized water, alkali gold is added
Slurries I is made in category source and rare earth metal source；Distilled water, phosphorus source, silicon source, silicon source are mixed by certain mol ratio, stirring, system
At gel II；Slurries I is poured into gel II, is stirred, template is added dropwise by certain mol proportion, stirring forms uniformly solidifying
Glue；Gel is added in reaction kettle, crystallization takes out cooling after a certain period of time, and filtration washing is dried at a certain temperature, in Muffle
Kiln roasting removed template method obtains.
Preferably, the silicon source be positive silicic acid second vinegar, positive silicic acid first vinegar, waterglass, Ludox or White Carbon black at least
It is a kind of；Source of aluminium is at least one of boehmite, aluminium isopropoxide, sodium metaaluminate, aluminum sulfate or aluminum nitrate；The mould
Plate agent is at least one of isopropylamine or triethylamine；Phosphorus source is phosphoric acid.
Preferably, wherein distilled water, phosphorus source, silicon source, silicon source and template mol ratio press 1~10：1~10:0.1~
1:10~100:1~10.
Preferably, ranging from 120~180 DEG C of crystallization temperature；Crystallization time ranging from 1~10 day.
Preferably, the content of two kinds of molecular sieves passes through H-NaZSM-5 and template in addition system in composite molecular screen
The mass ratio of DPA controls, and the mass ratio of the two is 1:1~5.
The present invention uses the HZSM-5/SAPO-11 molecular sieve catalysts of alkali metal and rare earth metal acid modification, is being catalyzed
When producing ethylene from dehydration of ethanol method, ethanol conversion and ethylene selectivity reach 99.9% or more, and successive reaction 100h, second
Alcohol conversion and ethylene selectivity are still maintained at 97%.
Specific implementation mode
Below in conjunction with the embodiment of the present invention, technical scheme in the embodiment of the invention is clearly and completely described,
Obviously, described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.Based in the present invention
The every other implementation that domain those of ordinary skill is obtained without making creative work is added in embodiment, ability
Example, shall fall within the protection scope of the present invention.
【Embodiment 1】
By a certain amount of commercially available H-NaZSM-5 molecular sieves and CeCl4It is added in deionized water and is sufficiently mixed with NaCl, be made
Slurries I；Sodium metaaluminate, phosphoric acid, 40% Ludox, distilled water are pressed into n (Al)：n(P)：n(Si):n(H2O) molar ratio is 1:
1:0.1:40 mixing, stir 20 minutes, obtain gel II；Slurries I is added in gel II, stirring 30 minutes, in molar ratio example n
(template)：N (P) is 2:1 is added template isopropylamine, continues stirring to homogeneous gel is formed, gel is fitted into reaction kettle,
170 DEG C of crystallization 1 day.Crystallization product chilling, filter, be washed to pH value be 8, in 120 DEG C dry 12 hours, in Muffle furnace in
550 DEG C of roasting removed template methods obtain synthetic catalyst A, so that the content of Ce in catalyst is by adjusting the dosage of each raw material
The content of 3.8%, Na of total catalyst weight is the 1.2% of total catalyst weight.
The performance evaluation that catalyst is carried out on atmospheric fixed bed reaction unit, uses internal diameter for 10 millimeters of stainless steel
Reactor, loaded catalyst are 10 milliliters, and reaction temperature is 260 DEG C, is reacted under normal pressure, and raw material is 80% ethyl alcohol, and air speed 6 is small
When‐1.Reaction product is analyzed respectively after gas-liquid separation, and reaction result is shown in Table 1.
【Embodiment 2】
By a certain amount of commercially available H-NaZSM-5 molecular sieves and YCl4It is added in deionized water and is sufficiently mixed with LiCl, be made
Slurries I；Sodium metaaluminate, phosphoric acid, 40% Ludox, distilled water are pressed into n (Al)：n(P)：n(Si):n(H2O) molar ratio is 1:
1:0.1:40 mixing, stir 20 minutes, obtain gel II；Slurries I is added in gel II, stirring 30 minutes, in molar ratio example n
(template)：N (P) is 2:1 is added template isopropylamine, continues stirring to homogeneous gel is formed, gel is fitted into reaction kettle,
170 DEG C of crystallization 1 day.Crystallization product chilling, filter, be washed to pH value be 8, in 120 DEG C dry 12 hours, in Muffle furnace in
550 DEG C of roasting removed template methods obtain synthetic catalyst B, so that the content of La in catalyst is by adjusting the dosage of each raw material
The content of 4.0%, Na of total catalyst weight is the 1.8% of total catalyst weight.
The performance evaluation that catalyst is carried out on atmospheric fixed bed reaction unit, uses internal diameter for 10 millimeters of stainless steel
Reactor, loaded catalyst are 10 milliliters, and reaction temperature is 240 DEG C, is reacted under normal pressure, and raw material is 80% ethyl alcohol, air speed 10
Hour‐1.Reaction 10h reaction products are analyzed respectively after gas-liquid separation, and reaction result is shown in Table 1.
【Embodiment 3】
By a certain amount of commercially available H-NaZSM-5 molecular sieves and LaCl4It is added in deionized water and is sufficiently mixed with KCl, be made
Slurries I；Sodium metaaluminate, phosphoric acid, 40% Ludox, distilled water are pressed into n (Al)：n(P)：n(Si):n(H2O) molar ratio is 1:
1:0.1:40 mixing, stir 20 minutes, obtain gel II；Slurries I is added in gel II, stirring 30 minutes, in molar ratio example n
(template)：N (P) is 2:1 is added template isopropylamine, continues stirring to homogeneous gel is formed, gel is fitted into reaction kettle,
170 DEG C of crystallization 1 day.Crystallization product chilling, filter, be washed to pH value be 8, in 120 DEG C dry 12 hours, in Muffle furnace in
550 DEG C of roasting removed template methods obtain synthetic catalyst C, so that the content of La in catalyst is by adjusting the dosage of each raw material
The content of 4.0%, Na of total catalyst weight is the 1.8% of total catalyst weight.
The performance evaluation that catalyst is carried out on atmospheric fixed bed reaction unit, uses internal diameter for 10 millimeters of stainless steel
Reactor, loaded catalyst are 10 milliliters, and reaction temperature is 290 DEG C, is reacted under normal pressure, and raw material is 50% ethyl alcohol, and air speed 8 is small
When‐1.Reaction 10h reaction products are analyzed respectively after gas-liquid separation, and reaction result is shown in Table 1.
【Comparative example 1】
It uses commercially available H-ZSM-5 molecular sieves for catalyst, the performance of catalyst is carried out on atmospheric fixed bed reaction unit
Evaluation uses internal diameter for 10 millimeters of stainless steel reactor, and loaded catalyst is 10 milliliters, and reaction temperature is 260 DEG C, normal pressure
Lower reaction, raw material are 80% ethyl alcohol, air speed 6 hours‐1.Reaction product is analyzed respectively after gas-liquid separation, and reaction result is shown in Table 1.
【Comparative example 2】
It uses commercially available SAPO-34 molecular sieves for catalyst, the performance of catalyst is carried out on atmospheric fixed bed reaction unit
Evaluation uses internal diameter for 10 millimeters of stainless steel reactor, and loaded catalyst is 10 milliliters, and reaction temperature is 260 DEG C, normal pressure
Lower reaction, raw material are 80% ethyl alcohol, air speed 6 hours‐1.Reaction product is analyzed respectively after gas-liquid separation, and reaction result is shown in Table 1.
Table 1
Above description has fully disclosed the specific implementation mode of the present invention.It should be pointed out that being familiar with the field
Technical staff is to any change for being done of specific implementation mode of the present invention all without departing from the range of claims of the present invention.
Correspondingly, the scope of the claims of the invention is also not limited only to previous embodiment.
Claims (7)
1. a kind of catalyst for producing ethylene from dehydration of ethanol, it is characterised in that：Alkali metal and rare earth metal while modified HZSM-5-
5/SAPO-11 composite molecular screens, wherein alkali metal account for the 1%~2% of total catalyst weight, and rare earth metal accounts for overall catalyst weight
3.5~4.8%；The preparation method of the catalyst is as follows：Commercial HZSM-5 molecular sieves are mixed with deionized water, alkali is added
Slurries I is made in source metal and rare earth metal source；Distilled water, phosphorus source, silicon source, silicon source are mixed by certain mol ratio, stirring,
Gel II is made；Slurries I is poured into gel II, is stirred, template is added dropwise by certain mol proportion, stirring forms uniformly solidifying
Glue；Gel is added in reaction kettle, crystallization takes out cooling after a certain period of time, and filtration washing is dried at a certain temperature, in Muffle
Kiln roasting removed template method obtains.
2. the catalyst according to claim 1 for producing ethylene from dehydration of ethanol, it is characterised in that：The alkali metal source choosing
From one or more in the hydrochloride or nitrate of lithium, sodium, potassium or rubidium.
3. the catalyst according to claim 1 for producing ethylene from dehydration of ethanol, it is characterised in that：The rare earth metal source
One or more hydrochlorides in scandium (Sc), yttrium (Y), lanthanum (La), cerium (Ce), praseodymium (Pr).
4. the catalyst according to claim 1 for producing ethylene from dehydration of ethanol, it is characterised in that：The silicon source is positive silicon
At least one of sour second vinegar, positive silicic acid first vinegar, waterglass, Ludox or White Carbon black；Source of aluminium is boehmite, isopropyl
At least one of aluminium alcoholates, sodium metaaluminate, aluminum sulfate or aluminum nitrate；The template is at least one in isopropylamine or triethylamine
Kind；Phosphorus source is phosphoric acid.
5. the catalyst according to claim 1 for producing ethylene from dehydration of ethanol, it is characterised in that：Wherein distilled water, phosphorus
Source, silicon source, silicon source press n (Al)：n(P)：n(Si):n(H2O) molar ratio is 1~10：1~10：0.1~1：10~100：1~
10。
6. the catalyst according to claim 1 for producing ethylene from dehydration of ethanol, it is characterised in that：The crystallization temperature model
Enclose is 120~180 DEG C；Crystallization time ranging from 1~10 day.
7. the catalyst according to claim 1 for producing ethylene from dehydration of ethanol, it is characterised in that：Two in composite molecular screen
The content of kind molecular sieve is controlled by the mass ratio of HZSM-5 and template in addition system, and the mass ratio of the two is 1:1~
5。
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