CN106076408A - N-alkene isomerization catalyst and its preparation method and application - Google Patents
N-alkene isomerization catalyst and its preparation method and application Download PDFInfo
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- CN106076408A CN106076408A CN201610417288.1A CN201610417288A CN106076408A CN 106076408 A CN106076408 A CN 106076408A CN 201610417288 A CN201610417288 A CN 201610417288A CN 106076408 A CN106076408 A CN 106076408A
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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
- 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
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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]
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- C—CHEMISTRY; METALLURGY
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- 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
- C07C5/2702—Catalytic processes not covered by C07C5/2732 - C07C5/31; Catalytic processes covered by both C07C5/2732 and C07C5/277 simultaneously
- C07C5/2708—Catalytic processes not covered by C07C5/2732 - C07C5/31; Catalytic processes covered by both C07C5/2732 and C07C5/277 simultaneously with crystalline alumino-silicates, e.g. molecular sieves
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- 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)
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Abstract
The present invention provides a kind of N-alkene isomerization catalyst, containing 50 90%(mass) molecular sieve, remaining is aluminium oxide；Described molecular sieve is made up of SAPO 11 and ZSM 5, and wherein SAPO 11 accounts for 75 90%(mass of molecular sieve total amount), ZSM 5 accounts for 10 25%(mass of molecular sieve total amount)；Microparticle size 1 2um of catalyst Middle molecule sieve.This catalyst has higher normal olefine isomerization activity, isomeric olefine yield is higher and can keep the long period, there is longer one way service cycle, repeatedly the coke burning regeneration performance range of decrease is less, be suitable to be prepared through isomerization reaction the process of isobutene. by n-butene, and prepared the process of iso-amylene through isomerization reaction by n-pentene, it is particularly well-suited to carbon four n-butene isomerization after ether, prepares the process of isobutene..
Description
Technical field
The invention belongs to catalyst field, relate to a kind of N-alkene isomerization catalyst and its preparation method and application.
Background technology
Methyl tertiary butyl ether(MTBE) (MTBE) is because demonstrating higher octane number, low steam in reformulated gasoline and oxygenated gasoline
Pressure, the favorable solubility in gasoline fraction hydro carbons, so becoming excellent gasoline addO-on therapy, its demand was rapid in recent years
Increase, traditional petroleum catalytic cracking and hot-working the isobutene. yield obtained is far from meeting the need that ether-based device produces
Want.
Produce the ether-based device outlet material of MTBE, after separating methanol and ether, positive structure butene content more than 40%, therefore
This is carried out skeletal isomerization rich in the material of n-butene and produces isobutene., can reach to increase production the purpose of isobutene..This technique is former
Expect cheap and easy to get, source is relatively wide, the overstock problem of linear alkene can be solved, can provide a large amount of containing isobutene. for ether-based device again
Raw material, only need to be at existing ether-based device added downstream olefin isomerization gasifying device, thus this technique obtains more answering in the recent period
With, newly-built or reconstructed carbon four isomerization unit after many sets ether.
N-butene skeletal isomerization is generally carried out on acidic catalyst, and catalyst includes that SAPO (SAPO) is
Row molecular sieve, ferrierite etc..Existing this kind of catalyst, the short time as all have in several days preferable n-butene conversion and
Selective isobutene, but performance declines rapidly afterwards, therefore one way is shorter for service cycle, needs frequent coke burning regeneration, and after burning
Performance easily declines.Existing more prior art proposes all improvement, but generally one way days of operation was less than 30 days, uses
Also tending to hydraulic performance decline after 1 year obvious, thus regeneration times is more, catalyst change is frequent, costly.
Summary of the invention
For solving above-mentioned technical problem, the present invention provides a kind of N-alkene isomerization catalyst, containing 50-90% (quality)
Molecular sieve, remaining is aluminium oxide；Described molecular sieve is made up of SAPO-11 and ZSM-5, and wherein SAPO-11 accounts for molecular sieve total amount
75-90% (quality), ZSM-5 account for the 10-25% (quality) of molecular sieve total amount；Microparticle size 1-of catalyst Middle molecule sieve
2um.This catalyst has higher normal olefine isomerization activity, and isomeric olefine yield is higher and can keep the long period, tool
Having longer one way service cycle, repeatedly the coke burning regeneration performance range of decrease is less, is suitable to be prepared different through isomerization reaction by n-butene
The process of butylene, and prepared the process of iso-amylene through isomerization reaction by n-pentene.
The N-alkene isomerization catalyst of the present invention, it is preferable that molecular sieve content 50-70% (quality)；Preferably,
SAPO-11 accounts for the 80-85% (quality) of molecular sieve total amount, and ZSM-5 accounts for the 15-20% (quality) of molecular sieve total amount.
The N-alkene isomerization catalyst of the present invention, it is preferable that ZSM-5 molecular sieve silica alumina ratio 40-70.
The N-alkene isomerization catalyst of the present invention, it is preferable that (quality) Han magnesium oxide 0.5-2.0% in molecular sieve.
Present invention also offers a kind of preparation method of described N-alkene isomerization catalyst, comprise the following steps:
A, material-compound tank add suitable quantity of water, adds the desired amount of SAPO-11 molecular screen primary powder, the former powder of ZSM-5 molecular sieve and hydrogen
Alumina powder, adds ammonium acetate, making beating, powder total concentration 10-20% (quality) in serosity, ammonium acetate concentration 0.5-2.0% (matter
Amount)；Described SAPO-11 molecular screen primary powder is the hydrogen type molecular sieve through Crystallizing treatment, is easily dispersed to mean diameter 1-2um；Institute
Stating the former powder of ZSM-5 molecular sieve is the hydrogen type molecular sieve through Crystallizing treatment, is easily dispersed to mean diameter 1-2um；
C, serosity proceed to autoclave, at 150-220 DEG C of Crystallizing treatment 10-60hr；
D, serosity are spray-dried, and xeraphium adds lubricant, adds containing extrusion after aqueous acid kneading, then drying, 550-600
DEG C roasting, prepares catalyst of the present invention.
The preparation method of N-alkene isomerization catalyst of the present invention, it is preferable that step D containing in aqueous acid, add
Magnesium acetate, is converted into magnesium oxide and accounts for the 0.5-2.0% (quality) of molecular sieve, more preferably account for 1.0% (quality) of molecular sieve.
The preparation method of N-alkene isomerization catalyst of the present invention, it is preferable that in step C, Crystallizing treatment temperature 170-
200 DEG C, process time 20-40hr.
The preparation method of N-alkene isomerization catalyst of the present invention, it is preferable that in step D, catalyst is at 560-580 DEG C
Roasting 2-4hr.
The preparation method of N-alkene isomerization catalyst of the present invention, it is preferable that before step C, the most in steps B: step
Rapid A serosity grinding distribution equipment processes further, makes powder microparticle refine to average diameter 1-2um.Described grinding distribution
Equipment is colloid mill or homogenizer, and wherein colloid mill is relatively cheap and conventional.
The preparation method of N-alkene isomerization catalyst of the present invention, it is preferable that in step A, described aluminium hydrate powder is
Boehmite dry powder；In step C, described acid is one or more in nitric acid, citric acid, acetic acid, and wherein acetic acid effect is relatively
Good.
N-alkene isomerization catalyst of the present invention, is particularly well-suited to carbon four n-butene isomerization after ether, prepares isobutene.
Process.During after ether, carbon four n-butene isomerization prepares isobutene., by controlling suitable technological parameter, the present invention is just
Structure olefin isomerization catalyst, under conditions of maintaining higher n-butene isomerization activity and higher isobutene. yield, tool
Having longer one way service cycle, can be usually reached more than 30 days, long reached 80 days.Compared to the prior art, one way fortune
Turning natural law to be obviously prolonged, the expense during stopping, burn and again going into operation reduces significantly.
N-alkene isomerization catalyst of the present invention, within longer one way service cycle, it is possible to maintain higher positive structure alkene
The reason of the active and higher isomeric olefine purpose product yield of hydrocarbon isomerization, it may be possible to preferably balance reactivity worth and resistive connection
Burnt, anti-carbon performance, potentially includes:
(1) SAPO-11 in catalyst, ZSM-5 molecular sieve microparticle size are less, and only 1-2um, microparticle external surface area is relatively
Greatly, thus the aperture of microparticle surfaces blocking forming process slower；Reactant and the product biography in duct between microparticle in microparticle
Matter is easier to；The size of existing similar catalyst Middle molecule sieve microparticle is usually above 2um；
(2) SAPO-11 molecular sieve is the major catalytic component of normal olefine isomerization reaction, and it is main that reactivity worth declines
Reason is coking and the duct carbon distribution of acid centre；The acidity of ZSM-5 molecular sieve is better than SAPO-11, the easy life in olefin feedstock
In burnt composition such as alkadienes, methanol or isomerization process, the alkadienes of by-product, dimer are easier at ZSM-5 molecular sieve microparticle
Middle coking, carbon distribution and consume, thus reduce the coking in SAPO-11 molecular sieve microparticle, carbon distribution, and make catalyst just
Structure olefin isomerization performance is maintained for a long time；
(3) SAPO-11 molecular screen primary powder, the former powder of ZSM-5 molecular sieve and the Crystallizing treatment of aluminium hydrate powder serosity, decrease
In molecular sieve, the quantity of acid stronger acid centre, reduces the speed of coking in molecular sieve microparticle, carbon distribution, decreases it
His side reaction, thus improve and maintain the yield of isomerization product.
N-alkene isomerization catalyst of the present invention, except having longer one way service cycle, catalytic performance is the most more
Stable, after repeatedly regeneration, the isomerization activity of normal olefine and the yield of isomeric olefine product decline less, and this point may
Secondary crystallization process with molecular sieve is relevant, and described secondary crystallization processes the structure making SAPO-11 molecular sieve, ZSM-5 molecular sieve
Become more stable with performance.
In the present invention, molecular screen primary powder mean diameter is recorded by laser particle analyzer, and before surveying, serosity carries out ultrasonic disperse, also leads to
Crossing electromicroscopic photograph (SEM) to compare, two kinds of results are basically identical；The flat of microparticle in rear slurry is processed with grinding distribution equipment
All diameters, in autoclave, the average diameter of microparticle in Crystallizing treatment rear slurry, is recorded by laser particle analyzer, and before surveying, serosity does not enters
Row ultrasonic disperse；The microparticle size of catalyst Middle molecule sieve, is judged by the electromicroscopic photograph (SEM) of catalyst surface, section.
Detailed description of the invention
Embodiment 1
Make former with the SAPO-11 molecular screen primary powder through Crystallizing treatment and the former powder of ZSM-5 molecular sieve through Crystallizing treatment
Material；SAPO-11 molecular screen primary powder is easily dispersed to mean diameter 1.2um, degree of crystallinity 95%, chemical composition P2O541%, SiO2
12%, Al2O347% (quality)；The former powder of ZSM-5 molecular sieve is easily dispersed to mean diameter 1.6um, silica alumina ratio 70, degree of crystallinity
95%.Catalyst be prepared as follows:
Adding 50kg deionized water in A, 60L material-compound tank, addition SAPO-11 molecular screen primary powder 2.0kg, ZSM-5 molecular sieve are former
Powder 0.5kg and boehmite dry powder 3.75kg, adds ammonium acetate 0.56kg, making beating；
C, serosity proceed to 100L autoclave, at 200 DEG C of Crystallizing treatment 20hr；
D, 200 DEG C of serosity spray drying, take xeraphium 5.0kg and add sesbania powder 0.15kg mixing, add containing acetic acid 0.20kg's
By Φ 2.0mm orifice plate extrusion after aqueous solution 4.5kg kneading, then through 120 DEG C of dry 6hr, 570 DEG C of roasting 4hr, prepare catalyst
3kg。
Calculating from ingredient proportion, the catalyst molecular sieve containing 50% (quality) obtained by the present embodiment, containing 50% (quality)
Aluminium oxide；SAPO-11 accounts for 80% (quality) of molecular sieve total amount, and ZSM-5 accounts for 20% (quality) of molecular sieve total amount.From catalysis
Agent surface, the electromicroscopic photograph (SEM) of section judge, microparticle size 1-2um of catalyst Middle molecule sieve.
Embodiment 2
Substantially with embodiment 1, difference is in the serosity of step A, SAPO-11 molecular screen primary powder addition 2.125kg,
ZSM-5 molecular sieve former powder addition 0.375kg.
Calculating from ingredient proportion, the catalyst molecular sieve containing 50% (quality) obtained by the present embodiment, containing 50% (quality)
Aluminium oxide；SAPO-11 accounts for 85% (quality) of molecular sieve total amount, and ZSM-5 accounts for 15% (quality) of molecular sieve total amount.From catalysis
Agent surface, the electromicroscopic photograph (SEM) of section judge, microparticle size 1-2um of catalyst Middle molecule sieve.
Embodiment 3
Substantially with embodiment 1, difference is in the serosity of step A, boehmite dry powder addition 1.60kg, Yi Jibu
In rapid D, take xeraphium 2.5kg and add sesbania powder 0.075kg mixing, add the aqueous solution 2.3kg containing acetic acid 0.10kg.
Calculating from ingredient proportion, the catalyst molecular sieve containing 70% (quality) obtained by the present embodiment, containing 30% (quality)
Aluminium oxide；SAPO-11 accounts for 80% (quality) of molecular sieve total amount, and ZSM-5 accounts for 20% (quality) of molecular sieve total amount.From catalysis
Agent surface, the electromicroscopic photograph (SEM) of section judge, microparticle size 1-2um of catalyst Middle molecule sieve.
Embodiment 4
Substantially with embodiment 1, difference is in the serosity of step A, boehmite dry powder addition 0.42kg, Yi Jibu
In rapid D, take xeraphium 2.5kg and add sesbania powder 0.075kg mixing, add the aqueous solution 2.5kg containing acetic acid 0.10kg.
Calculating from ingredient proportion, the catalyst molecular sieve containing 90% (quality) obtained by the present embodiment, containing 10% (quality)
Aluminium oxide；SAPO-11 accounts for 80% (quality) of molecular sieve total amount, and ZSM-5 accounts for 20% (quality) of molecular sieve total amount.From catalysis
Agent surface, the electromicroscopic photograph (SEM) of section judge, microparticle size 1-2um of catalyst Middle molecule sieve.
Embodiment 5
Substantially with embodiment 1, difference be step D containing in aqueous acid, add four water magnesium acetate 0.135kg, be converted into
Magnesium oxide accounts for 1.0% (quality) of molecular sieve.
Calculating from ingredient proportion, the catalyst molecular sieve containing 50% (quality) obtained by the present embodiment, containing 50% (quality)
Aluminium oxide；SAPO-11 accounts for 80% (quality) of molecular sieve total amount, and ZSM-5 accounts for 20% (quality) of molecular sieve total amount, molecular sieve
In another containing magnesium oxide 1.0% (quality).Judge from the electromicroscopic photograph (SEM) of catalyst surface, section, catalyst Middle molecule sieve
Microparticle size 1-2um.
Embodiment 6
Substantially with embodiment 2, difference be step D containing in aqueous acid, four water magnesium acetate additions 0.068kg, folding
Magnesium oxide is become to account for 0.5% (quality) of molecular sieve.
Calculating from ingredient proportion, the catalyst molecular sieve containing 50% (quality) obtained by the present embodiment, containing 50% (quality)
Aluminium oxide；SAPO-11 accounts for 85% (quality) of molecular sieve total amount, and ZSM-5 accounts for 15% (quality) of molecular sieve total amount, molecular sieve
In another containing magnesium oxide 0.5% (quality).Judge from the electromicroscopic photograph (SEM) of catalyst surface, section, catalyst Middle molecule sieve
Microparticle size 1-2um.
Embodiment 7
Substantially with embodiment 2, difference be step D containing in aqueous acid, four water magnesium acetate additions 0.27kg, be converted into
Magnesium oxide accounts for 2.0% (quality) of molecular sieve.
Calculating from ingredient proportion, the catalyst molecular sieve containing 50% (quality) obtained by the present embodiment, containing 50% (quality)
Aluminium oxide；SAPO-11 accounts for 85% (quality) of molecular sieve total amount, and ZSM-5 accounts for 15% (quality) of molecular sieve total amount, molecular sieve
In containing magnesium oxide 2.0% (quality).Judging from the electromicroscopic photograph (SEM) of catalyst surface, section, it is micro-that catalyst Middle molecule sieves
Particle size 1-2um.
Embodiment 8
Substantially with embodiment 1, difference is in step C, Crystallizing treatment temperature 180 DEG C, processes time 30hr.
Judge from the electromicroscopic photograph (SEM) of catalyst surface, section, microparticle size 1-2um of catalyst Middle molecule sieve.
Embodiment 9
Substantially with embodiment 1, difference is in step C, Crystallizing treatment temperature 170 DEG C, processes time 40hr.
Judge from the electromicroscopic photograph (SEM) of catalyst surface, section, microparticle size 1-2um of catalyst Middle molecule sieve.
Embodiment 10
Substantially with embodiment 1, difference is before step C, B the most in steps: step A serosity colloid mill is ground
Dispersion processes, and makes powder microparticle refine to average diameter 1.7um.
The average diameter of microparticle in Crystallizing treatment rear slurry in autoclave, laser particle analyzer surveys 1.9um；Catalyst divides
The microparticle size of son sieve, catalyst surface, the electromicroscopic photograph (SEM) of section are shown as 1-2um.
Embodiment 11
Basic with embodiment 1, but combine embodiment 5, the method for embodiment 10, step A serosity colloid mill is carried out
Grinding distribution processes, and makes powder microparticle refine to average diameter 1.8um；Step D containing in aqueous acid, add four water acetic acid
Magnesium 0.135kg, is converted into magnesium oxide and accounts for 1.0% (quality) of molecular sieve.
The average diameter of microparticle in Crystallizing treatment rear slurry in autoclave, laser particle analyzer surveys 1.9um；Catalyst divides
The microparticle size of son sieve, catalyst surface, the electromicroscopic photograph (SEM) of section are shown as 1-2um.
Embodiment 12
Substantially with embodiment 1, difference is to have employed another kind of SAPO-11 molecular screen primary powder, and it is easily dispersed to average particle
Footpath 1.7um, degree of crystallinity 95%, chemical composition P2O542%, SiO215%, Al2O343% (quality).
Calculating from ingredient proportion, the catalyst molecular sieve containing 50% (quality) obtained by the present embodiment, containing 50% (quality)
Aluminium oxide；SAPO-11 accounts for 80% (quality) of molecular sieve total amount, and ZSM-5 accounts for 20% (quality) of molecular sieve total amount.From catalysis
Agent surface, the electromicroscopic photograph (SEM) of section judge, microparticle size 1-2um of catalyst Middle molecule sieve.
Embodiment 13
Substantially with embodiment 1, difference is to have employed the another kind of former powder of ZSM-5 molecular sieve, and it is easily dispersed to mean diameter
1.3um, silica alumina ratio 40, degree of crystallinity 95%.
Calculating from ingredient proportion, the catalyst molecular sieve containing 50% (quality) obtained by the present embodiment, containing 50% (quality)
Aluminium oxide；SAPO-11 accounts for 80% (quality) of molecular sieve total amount, and ZSM-5 accounts for 20% (quality) of molecular sieve total amount.From catalysis
Agent surface, the electromicroscopic photograph (SEM) of section judge, microparticle size 1-2um of catalyst Middle molecule sieve.
Comparative example 1
Substantially with embodiment 1, difference is the Crystallizing treatment not having step C.
Comparative example 2
Substantially with embodiment 5, difference is the Crystallizing treatment not having step C.
Comparative example 3
Substantially with embodiment 10, difference is the Crystallizing treatment not having step C.
Comparative example 4
Substantially with embodiment 1, difference is in step A not add the former powder of ZSM-5 molecular sieve, SAPO-11 molecular screen primary
Powder is 2.5kg.
From the surface of catalyst each prepared by embodiment 1-13, section electromicroscopic photograph (SEM), catalyst Middle molecule sieve
Microparticle size 1-2um, and the particle diameter situation difference of SAPO-11 molecular screen primary powder, the former powder of ZSM-5 molecular sieve is inconspicuous.
The XRD figure of each catalyst prepared by embodiment 1,5,11,12,13 composed, the XRD figure of comparative example 1,2 catalyst is composed
Carry out, and the XRD figure spectrum of SAPO-11 molecular screen primary powder, the former powder of ZSM-5 molecular sieve compares repeatedly, it is judged that think embodiment
1, SAPO-11 molecular sieve, the structure of ZSM-5 molecular sieve in 5,11,12,13 catalyst, and do not carry out secondary crystallization process
The structure of SAPO-11 molecular sieve, ZSM-5 molecular sieve in comparative example catalyst, with SAPO-11 molecular screen primary powder, ZSM-5 molecular sieve
The structure of former powder is compared, and distinguishes inconspicuous, and other kinds of molecular sieve structure does not occur.This explanation, in above-mentioned condition
Under in the Crystallizing treatment that carries out and subsequent catalyst preparation process, SAPO-11 molecular sieve, the structure of ZSM-5 molecular sieve are protected substantially
Hold, and do not generate other kinds of molecular sieve.
Evaluation test 1
Embodiment 1-13, each catalyst of comparative example 1-4 are carried out laboratory evaluation respectively, and evaluation response is continuous in fixed bed
Carry out on micro-reaction equipment, tube inner diameter 15mm, catalyst breakage to particle diameter 0.6-0.8mm (20-30 mesh), loadings
10ml；Measuring liquid with the continuous rill of carbon after ether four and the continuous flow produced that all gasifies makees unstripped gas, raw material forms such as table 1 institute
Row, reaction pressure 0.135MPa, according to carbon after ether four steel cylinder loss of weight be located at the gas rotameter before reaction tube and control former
Material throughput, gas space velocity 800hr-1；Evaluation response outlet expects to collect into-18 DEG C of refrigerator coolings.
After after ether, carbon four unstripped gas feeds intake, bed temperature 1-3hr controls 280 DEG C or less, after 3hr, according to outlet
In thing, the yield situation of isobutene. controls, and gradually heats up, and makes isobutene. yield close to or up 40-41%, controls bed after 10hr
Layer temperature makes isobutene. yield 40-41%.Each catalyst bed temperature situation when evaluation time 50,100hr is listed in table
2, with during identical evaluation time with bed temperature junior for excellent；By each catalyst n-butene when evaluation time 50,100hr
Conversion ratio, isobutene. yield, isomerized oil yield situation are listed in table 2.
After ether, carbon four raw material and evaluation response outlet material, with two gas Chromatographic Determination compositions, all use Liquid sample introduction, liquid
Body and injector are all pre-chilled to-18 DEG C.One chromatograph carbon determination four and following components, capillary column AT.PLOT aluminium oxide/S, 50m*
0.53mm*20um, detector FID, heat up after constant temperature purging；The main carbon determination of another chromatograph five and above component (carbon five+, isomery
Carburetion), capillary column OV-1,50m*0.53mm*5 μm, detector FID, temperature programming；Two chromatographic datas by carbon four and with
The content of lower component is fitted, and determines carbon one to carbon 12 constituent content.2-5hr surveys once per hour, 5-10hr is every
Within two hours, survey once, 10-50hr surveys once for every four hours, 50-100hr surveys once for every six hours.
When needing to measure gas composition once in a while, evaluation response outlet material is not entered refrigerator and directly room temperature take gas sample introduction.
In evaluation response outlet material, hydrogen content is carried out by the gas chromatogram equipped with 13X packed column and thermal conductivity detector (TCD),
But during each catalyst 100hr evaluates, the hydrogen content of institute's measured reaction outlet material is all less than 0.05% (volume).
Isobutene. yield=n-butene conversion X selective isobutene.
Isomerized oil yield=n-butene conversion X carbon five+selectivity
From table 2-3 data it can be seen that although the secondary crystallization of molecular sieve, aluminium hydroxide mixed serum processes and makes molecular sieve
Activity slightly reduce, but significantly reduce the deactivation rate of catalyst, extend the life-span of catalyst, molecular sieve introduces oxygen
Change magnesium and also play similar effect；The introducing of ZSM-5 molecular sieve, has been significantly reduced the deactivation rate of catalyst, has carried simultaneously
The high conversion ratio of n-butene, and generate the isomerized oil of higher-value, this isomerized oil main component is carbon eight, octane number
Higher than MTBE, gasoline component can be directly used as.
Carbon four raw material composition, V% after table 1 ether
| Propane | 0.07 |
| Propylene | 0.02 |
| Iso-butane | 35.37 |
| Normal butane | 10.03 |
| Trans-butene-2 | 21.47 |
| Butene-1 | 15.95 |
| Isobutene. | 0.05 |
| Cis-butene-2 | 16.65 |
| Total amylene | 0.13 |
| Butadiene | 0.012 |
| Methanol | 0.008 |
| Sulfur content | 0.005 |
| N-butene amounts to | 54.07 |
Table 2 is the reaction bed temperature of the different durations of runs under the conditions of controlling isobutene. yield 40-41%
| Catalyst | 50hr bed temperature, DEG C | 100hr bed temperature, DEG C |
| Embodiment 1 | 330 | 332 |
| Embodiment 2 | 329 | 331 |
| Embodiment 3 | 324 | 326 |
| Embodiment 4 | 320 | 323 |
| Embodiment 5 | 332 | 333 |
| Embodiment 6 | 329 | 331 |
| Embodiment 7 | 332 | 335 |
| Embodiment 8 | 330 | 331 |
| Embodiment 9 | 331 | 333 |
| Embodiment 10 | 328 | 330 |
| Embodiment 11 | 331 | 332 |
| Embodiment 12 | 334 | 336 |
| Embodiment 13 | 331 | 334 |
| Comparative example 1 | 318 | 324 |
| Comparative example 2 | 322 | 327 |
| Comparative example 3 | 315 | 321 |
| Comparative example 4 | 326 | 334 |
Table 3 evaluates 50,100hr time n-butene conversion, isobutene. yield, isomerized oil yield situation
Evaluation test 2
Embodiment 1,5,10,11 catalyst and comparative example 1,4 catalyst are carried out respectively industry side line evaluation test.Reaction
Bore 100mm, catalyst without broken, Φ 1.8X 3-6mm, loadings 3000ml, bed height 410mm, bed sets
The Φ 3mm porcelain ball of 1000mm height is as preheating section；Beds sets three points for measuring temperature, and thermocouple is loaded on and is fixed on reaction tube
In the sleeve pipe of axis；Reaction tube peripheral hardware copper pipe samming, is heating furnace body outside copper pipe.Continuously, all gasify with carbon after ether four institute
The continuous flow produced makees unstripped gas, and raw material composition is surveyed once every day, substantially with table 1 listed by identical, reaction pressure controls 0.12-
0.13MPa, controls raw gas flow according to the gas rotameter before being located at reaction tube, and reaction tube outlet is expected into steel cylinder, steel
Bottle can put into-18 DEG C of refrigerators or taking-up, sets coil pipe and sample tap before steel cylinder entrance.
Control gas space velocity 400hr-1；Bed temperature 1-3hr controls less than 280 DEG C, after 3hr, according in outlet thing
The yield situation of isobutene. controls, and gradually heats up, suitably controls reaction bed temperature after 10hr, makes isobutene. yield as far as possible
For 40-41%.
2-5hr surveys once per hour, every two hours of 5-10hr surveys once, 10-50hr surveys once for every four hours, the
50-100hr surveys once for every six hours, within after 100hr every six hours, surveys once.
The assay method of outlet material sample is identical with evaluation test 1.
In evaluation response outlet material, below 0.05% (volume) before hydrogen content 1000hr, terminates below to evaluating
0.10% (volume).
Described embodiment 1,5,10,11 catalyst, the operating side line evaluation of its first one way, result is as listed by table 4,5.
Table 4 catalyst one way operating side line evaluation result
Table 5 catalyst one way operating side line evaluation result
After one way operating terminates, coke burning regeneration, continuously run, burn four times, catalyst performance declines less, the 4th list
Journey duration of runs, only reduce 10-13%, n-butene conversion, isobutene. yield, isomerization the duration of runs relative to first one way
Oil yield situation is basically unchanged.
Described comparative example 1,4 catalyst, the operating side line evaluation of its first one way, result is as listed by table 6.
Table 6 catalyst one way operating side line evaluation result
Table 4-6 result shows, molecular sieve, the secondary crystallization of aluminium hydroxide mixed serum process, hence it is evident that reduce catalyst
Deactivation rate, extend the life-span of catalyst, in molecular sieve introduce magnesium oxide also play similar effect；ZSM-5 molecule
The introducing of sieve, has been significantly reduced the deactivation rate of catalyst, has improve the conversion ratio of n-butene simultaneously, and generate higher price
The isomerized oil of value.
Claims (10)
1. a N-alkene isomerization catalyst, containing the molecular sieve of 50-90% (quality), remaining is aluminium oxide；Described molecule
Sieve is made up of SAPO-11 and ZSM-5, and wherein SAPO-11 accounts for the 75-90% (quality) of molecular sieve total amount, and it is total that ZSM-5 accounts for molecular sieve
The 10-25% (quality) of amount.
2. N-alkene isomerization catalyst as claimed in claim 1, it is characterised in that SAPO-11 accounts for molecular sieve total amount
80-85% (quality), ZSM-5 account for the 15-20% (quality) of molecular sieve total amount.
3. N-alkene isomerization catalyst as claimed in claim 1, it is characterised in that molecular sieve content 50-70% (matter
Amount).
4. arbitrary N-alkene isomerization catalyst as described in claim 1-3, it is characterised in that containing magnesium oxide in molecular sieve
0.5-2.0% (quality).
5. the preparation method of N-alkene isomerization catalyst as described in claim 1-4, comprises the following steps:
A, material-compound tank add suitable quantity of water, adds the desired amount of SAPO-11 molecular screen primary powder, the former powder of ZSM-5 molecular sieve and hydroxide
Aluminium powder, adds ammonium acetate, making beating, powder total concentration 10-20% (quality) in serosity, ammonium acetate concentration 0.5-2.0% (quality)；
C, proceed to autoclave, at 150-240 DEG C of Crystallizing treatment 10-60hr；
D, step C serosity are spray-dried, and xeraphium adds lubricant, adds containing extrusion after aqueous acid kneading, then drying, roasting,
Prepare catalyst of the present invention.
6. the preparation method of N-alkene isomerization catalyst as claimed in claim 5, it is characterised in that in the serosity of step A,
Add magnesium acetate, be converted into magnesium oxide and account for the 0.5-2.0% (quality) of molecular sieve.
7. the preparation method of N-alkene isomerization catalyst as claimed in claim 5, it is characterised in that in step C, at crystallization
Reason temperature 170-200 DEG C, processes time 20-40hr.
8. the preparation method of N-alkene isomerization catalyst as claimed in claim 5, it is characterised in that in step D, catalyst
At 560-580 DEG C of roasting 2-4hr.
9. the preparation method of arbitrary N-alkene isomerization catalyst as described in claim 5-8, it is characterised in that in step C
Before, B the most in steps: step A serosity grinding distribution equipment processes further, makes powder microparticle refine to average diameter 1-
2um。
10. N-alkene isomerization catalyst carbon four n-butene isomerization after by ether prepares isobutene. as claimed in claim 1
During application.
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| CN106040293A (en) * | 2016-06-13 | 2016-10-26 | 山东迅达化工集团有限公司 | N-alkene isomerization catalyst, method for preparing same and application of n-alkene isomerization catalyst |
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| CN101081370A (en) * | 2006-05-31 | 2007-12-05 | 中国石油大学(北京) | ZSM-5/SAPO-11 composite zeolite and catalytically cracked gasoline hydrogenation quality-improved catalyzer and the methoer for preparing the same |
| CN103566966A (en) * | 2012-08-03 | 2014-02-12 | 中国石油化工股份有限公司 | N-alkene isomerization catalyst and preparation method thereof |
| CN104117388A (en) * | 2013-04-23 | 2014-10-29 | 上海碧科清洁能源技术有限公司 | SAPO-11/ZSM-5 mixed molecular-sieve catalyst, and preparation and application thereof |
| CN106040293A (en) * | 2016-06-13 | 2016-10-26 | 山东迅达化工集团有限公司 | N-alkene isomerization catalyst, method for preparing same and application of n-alkene isomerization catalyst |
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