CN103772108B - The method of fluidized bed olefin disproportionation propylene - Google Patents
The method of fluidized bed olefin disproportionation propylene Download PDFInfo
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- CN103772108B CN103772108B CN201210412603.3A CN201210412603A CN103772108B CN 103772108 B CN103772108 B CN 103772108B CN 201210412603 A CN201210412603 A CN 201210412603A CN 103772108 B CN103772108 B CN 103772108B
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Abstract
The present invention relates to a kind of method of fluidized bed olefin disproportionation propylene, mainly solve the problem that there is the quick coking and deactivation of catalyzer in conventional art.The present invention is by adopting the method for fluidized bed olefin disproportionation propylene, and with ethene and butylene for raw material, be 320 ~ 500 DEG C in temperature of reaction, reaction pressure counts 0 ~ 1MPa with absolute pressure, and weight space velocity is 1 ~ 20 hour
-1condition under, raw material and fluid catalyst contact reacts generate the logistics containing propylene, fluid catalyst wherein used comprises following component with weight parts: a) Tungsten oxide 99.999 of 1 ~ 20 part, b) technical scheme of silica support of 80 ~ 99 parts, solve this problem preferably, can be used for the industrial production of preparing propylene through olefin disproportionation.
Description
Technical field
The present invention relates to a kind of method of fluidized bed olefin disproportionation propylene.
Background technology
The demand of the basic chemical raw materials such as propylene, ethene constantly increases, and crude oil material is day by day deteriorated, brings propylene and ethylene to produce contradiction.On the other hand, mixed c 4 and above alkene, alkane are the by-product of ethylene plant, refinery FCC apparatus and methanol-to-olefins, gasoline apparatus, usually can only as low value-added products such as liquefied gas as fuel.Utilize these olefin feedstocks to carry out further deep processing and produce high value added product propylene and ethene, made full use of the precious resources that this part is a considerable number of, there is extremely important meaning.
Olefin metathesis (Olefin metathesis) is a kind of conversion of olefines process.By under the effect of transition-metal catalyst (as W, Mo, Re etc.), in alkene C=C double bond fracture and again formed, thus new olefin product can be obtained.We can represent the dismutation of alkene simply from following reaction formula:
R in reaction formula
1, R
2, R
3, R
4represent different alkyl or hydrogen atom respectively.If wherein the disproportionation reaction (such as formula 1) of same alkene is called self disproportionation (self-metathesis); Disproportionation reaction (formula 2) between different alkene is then called cross disproportionation (cross-metathesis).
CN02137461.9 proposes the fixed bed catalyst for producing propene from butylene by disproportion, and catalyzer is WO
3/ SiO
2inert support, also containing the oxide compound 0.1 ~ 5% being selected from rhenium or magnesium in catalyzer., the catalyzer prepared by aforesaid method can make butylene disproportionation generate propylene; The yield of evaluation result display propylene is 24%, and the life-span is 420 hours.。
CN200310108173 reports the preparation method of olefin disproportionation catalyst, and its catalyzer consists of tungsten and oxide compound thereof, Cu and its oxides and carrier silicas.The catalyzer prepared by aforesaid method can be made butylene disproportionation react and generate propylene in fixed-bed reactor, and be 25% to the evaluation result display propene yield of catalyzer, the life-span is 470 hours.
When the reaction for preparing propylene through olefin disproportionation, all there is the problem that the quick coking and deactivation of catalyzer makes catalyst life short in the method in above document.
Summary of the invention
Technical problem to be solved by this invention there is the problem that the quick coking and deactivation of catalyzer makes the life-span short in prior art, and provide a kind of method of new fluidized bed olefin disproportionation propylene, the method has the advantage of catalyzer long service life.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of method of fluidized bed olefin disproportionation propylene, with ethene and butylene for raw material, is 320 ~ 500 DEG C in temperature of reaction, reaction pressure counts 0 ~ 1MPa with absolute pressure, and weight space velocity is 1 ~ 20 hour
-1condition under, raw material and fluid catalyst contact reacts generate the logistics containing propylene, and fluid catalyst wherein used comprises following component with weight parts: a) Tungsten oxide 99.999 of 1 ~ 20 part; B) silica support of 80 ~ 99 parts.
In technique scheme, the preferred version of the mol ratio of ethene and butylene is 1 ~ 4, and more preferably scheme is 2 ~ 3; The preferred version of temperature of reaction is 380 ~ 450 DEG C; The preferred version of reaction pressure is 0.4 ~ 0.6MPa; The preferred version of weight space velocity is 4 ~ 8 hours
-1; Tungsten oxide 99.999 is 2 ~ 16 parts with the preferred version of weight parts consumption, and more preferably scheme is 4 ~ 12 parts, and the preferred version of catalyzer is also comprise the lanthanum trioxide of 1 ~ 2 part and the zirconium white of 1 ~ 3 part with weight parts.
The preparation technology of catalyzer comprises slurrying, spraying is shaped, roasting three step.Usually first mesopore molecular sieve carrier is added appropriate deionized water to soak, add active ingredient tungsten source simultaneously, then stir with high-shear making beating, then add the binding agent of required amount.For intensity and the performance of catalyzer, the reinforced order of various raw material changes the difference that there is no greatly, thus can regulate arbitrarily reinforced order as required.Slurry prepared is like this uniform suspension, generally can place 24 hours and not obvious layering.
The solid content of usual slurry is 25 ~ 45%, is to reduce evaporation of water amount, reduces energy consumption, and solid content should be tried one's best height.Slurry is under inlet temperature 600 DEG C, outlet 350 DEG C of conditions, and spray drying granulation is shaping, must containing the microsphere particle of a small amount of water, then 600 DEG C of roastings 4 hours in retort furnace.
Obtained microsphere particle catalyzer is dry obtains catalyst sample.By sample by standard test abrasion index, bulk density and granularity, test its physical and chemical indexes.
Prepared catalyzer is the spheroidal particle of 30 ~ 100 microns, and median size is 60 microns, bulk density 0.6 ~ 0.8 kg/liter, and abrasion index is 0.5 ~ 0.7% hour
-1.
In the present invention, tungsten source can be the one in wolframic acid, sodium wolframate, ammonium tungstate, ammonium metawolframate, and good tungsten source is ammonium metawolframate.
Catalyzer prepared by technique scheme is for fluidized bed olefin disproportionation reaction, and the embodiment of the present invention is that ethene and butylene disproportionation generate propylene.Reaction conditions is as follows: in fluidized bed reactor, and temperature of reaction is 320 ~ 500 DEG C, and reaction pressure counts 0 ~ 1MPa with absolute pressure, and the mass space velocity of butylene is 1 ~ 20 hour
-1.
In such scheme, carbon four raw material can be the mixture of butene-1, butene-2 or butane, or from the C-4-fraction of steam cracking device.
The present invention is by adopting fluid catalyst, be conducive to raw material olefin to diffuse to catalyzer and carry out reacting and the quick desorption of propylene, slight coking is unlikely to complete blocking catalyst duct, and the toxic poisoning of catalyzer can be delayed, the heat dispersing when air burn regenerates, prevent molecular sieve structure avalanche, adopt lanthanum and zirconium as the auxiliary agent of disproportionation catalyst simultaneously, select suitable consumption, achieve unforeseeable technique effect, compare the catalyst activity not adding lanthanum and zirconium to be significantly improved, but the consumption of lanthanum and zirconium is unsuitable too high, the too high disproportionation that can suppress is active, also unsuitable too low, the too low effect not having modification.Adopt method of the present invention, in a fluidized bed reactor, temperature of reaction is 320 ~ 500 DEG C, and reaction pressure counts 0 ~ 1MPa with absolute pressure, butylene mass space velocity be 1 ~ 20 hour
-1under condition, by catalyzer and reaction raw materials contact reacts, the transformation efficiency of its butylene can reach 65%, the weight yield of propylene can reach 28%, the yield that ratio fixed bed catalyst is obtained by reacting is high by 3%, the life-span of catalyzer can reach 900 hours, time less than the life-span length 400 of fixed bed reaction catalyzer, achieves good technique effect.
Below by embodiment, the present invention is further elaborated.
Embodiment
[embodiment 1]
1 kilogram of silicon oxide is added in 2 kilograms of deionized waters and soak 10 minutes, pull an oar and add containing 63 grams of ammonium metatungstate solutions 200 grams after 10 minutes, finally add 200 grams of silicon sol (silica content 40%) making beating 15 minutes, obtain the slurry of 40% solid content.By this slurry import air temperature 600 DEG C, go out one's intention as revealed in what one says 350 DEG C of condition spraying dry and be shaped, then roasting makes catalyzer in 4 hours at retort furnace 600 DEG C, the median size of catalyzer is 60 microns, the bulk density of detecting catalyst and abrasion index, the results list 1.
Catalyzer 30 grams is arranged in the fluidized-bed reactor of Φ 30, appreciation condition and the results list 2.
[embodiment 2]
1 kilogram of silicon oxide is added in 2 kilograms of deionized waters and soak 10 minutes, to pull an oar the solution 200 grams added after 10 minutes containing 63 grams of ammonium metawolframates, 30 grams of lanthanum nitrates, 31 grams of zirconium nitrates, finally add 200 grams of silicon sol (silica content 40%) making beating 15 minutes, obtain the slurry of 40% solid content.By this slurry import air temperature 600 DEG C, go out one's intention as revealed in what one says 350 DEG C of condition spraying dry and be shaped, then roasting makes catalyzer in 4 hours at retort furnace 600 DEG C, the median size of catalyzer is 60 microns, the bulk density of detecting catalyst and abrasion index, the results list 1.
Catalyzer 30 grams is arranged in the fluidized-bed reactor of Φ 30, appreciation condition and the results list 2.
[embodiment 3]
1 kilogram of silicon oxide is added in 2 kilograms of deionized waters and soak 10 minutes, to pull an oar the solution 200 grams added after 10 minutes containing 63 grams of ammonium metawolframates, 60 grams of lanthanum nitrates, 93 grams of zirconium nitrates, finally add 200 grams of silicon sol (silica content 40%) making beating 15 minutes, obtain the slurry of 40% solid content.By this slurry import air temperature 600 DEG C, go out one's intention as revealed in what one says 350 DEG C of condition spraying dry and be shaped, then roasting makes catalyzer in 4 hours at retort furnace 600 DEG C, the median size of catalyzer is 60 microns, the bulk density of detecting catalyst and abrasion index, the results list 1.
Catalyzer 30 grams is arranged in the fluidized-bed reactor of Φ 30, appreciation condition and the results list 2.
[embodiment 4 ~ 8]
With the preparation process that embodiment 1 is identical, only change different components ratio and obtain different catalysts, catalyzer median size is all 60 microns, the bulk density of detecting catalyst and abrasion index, the results list 1.
Catalyzer 30 grams is arranged in the fluidized-bed reactor of Φ 30, appreciation condition and the results list 2.
[embodiment 9]
With the preparation process that embodiment 1 is identical, in ammonium metatungstate solution, only add 6 grams of ammonium dimolybdates, obtained catalyzer median size is all 60 microns, the bulk density of detecting catalyst and abrasion index, the results list 1.
Catalyzer 30 grams is arranged in the fluidized-bed reactor of Φ 30, appreciation condition and the results list 2.
Table 1
Note: wherein the catalyzer of example 2 is also containing 1 part of lanthanum trioxide and 1 part of zirconium white, the catalyzer of example 3 is also containing 2 parts of lanthanum trioxides and 3 parts of zirconium whites.
Table 2
Note: pressure is in absolute pressure.
[comparative example 1]
Taking ammonium metawolframate 63 grams adds in 2 kilograms of deionized waters, pour 1 kilogram of silicon oxide after being uniformly dissolved into, add 200 grams of silicon sol uniform stirring simultaneously, after stirring for some time, add the field mountain valley with clumps of trees and bamboo powder of 1%, after kneading, extrusion, drying, roasting 4 hours at 600 DEG C, obtains finished catalyst.
Catalyzer 30 grams is arranged in the fixed-bed reactor of Φ 30, appreciation condition and result as shown in table 3, be designated as B-1.
[comparative example 2 ~ 3]
With the preparation process that comparative example 1 is identical, only change different components ratio and obtain different catalysts.
Catalyzer 30 grams is arranged in the fixed-bed reactor of Φ 30, appreciation condition and result as shown in table 3, be designated as B-2 and B-3.
[comparative example 4 ~ 5]
With the preparation process that embodiment 2 is identical, only change the add-on of lanthanum nitrate and zirconium nitrate.
Catalyzer 30 grams is arranged in the fixed-bed reactor of Φ 30, appreciation condition and result as shown in table 3, be designated as B-4 and B-5.
Table 3
| Example | Tungsten oxide content (number) | Temperature (DEG C) | Weight space velocity (h -1) | Pressure (MPa) | Ethylene/butylene (mol ratio) | Butene conversion (%) | Propylene weight yield (%) | Life-span (h) |
| 1 | 4 | 380 | 4 | 1 | 2 | 64.6 | 28.8 | 930 |
| 2 | 4 | 380 | 4 | 1 | 2 | 70.6 | 30.8 | 1100 |
| 3 | 4 | 380 | 4 | 1 | 2 | 70.2 | 30.6 | 1150 |
| 4 | 1 | 450 | 10 | 0.6 | 1 | 65.2 | 28.4 | 850 |
| 5 | 16 | 320 | 1 | 0.5 | 2 | 65.7 | 28.5 | 920 |
| B-1 | 4 | 380 | 4 | 1 | 2 | 60.4 | 24.8 | 530 |
| B-2 | 1 | 450 | 10 | 0.6 | 1 | 61.7 | 25.2 | 520 |
| B-3 | 16 | 320 | 1 | 0.5 | 2 | 61.2 | 24.9 | 510 |
| B-4 | 4 | 380 | 4 | 1 | 2 | 64.0 | 27.8 | 720 |
| B-5 | 4 | 380 | 4 | 1 | 2 | 64.2 | 27.6 | 750 |
Note: wherein in comparative example 4 (B-4), the consumption of lanthanum trioxide is 0.8 part, and zirconic consumption is 0.8 part;
In comparative example 5 (B-5), the consumption of lanthanum trioxide is 2.5 parts, and zirconic consumption is 3.2 parts.
Claims (7)
1. a method for fluidized bed olefin disproportionation propylene, with ethene and butylene for raw material, be 320 ~ 500 DEG C in temperature of reaction, reaction pressure counts 0 ~ 1MPa with absolute pressure, and weight space velocity is 1 ~ 20 hour
-1condition under, raw material and fluid catalyst contact reacts generate the logistics containing propylene, and fluid catalyst wherein used comprises following component with weight parts:
A) Tungsten oxide 99.999 of 1 ~ 20 part;
B) silica support of 80 ~ 99 parts;
Described fluid catalyst also comprises the lanthanum trioxide of 1 ~ 2 part and the zirconium white of 1 ~ 3 part with weight parts.
2. the method for a kind of fluidized bed olefin disproportionation propylene according to claim 1, is characterized in that the mol ratio of ethene and butylene is 1 ~ 4.
3. the method for a kind of fluidized bed olefin disproportionation propylene according to claim 1, is characterized in that temperature of reaction is 380 ~ 450 DEG C.
4. the method for a kind of fluidized bed olefin disproportionation propylene according to claim 1, is characterized in that reaction pressure is 0.4 ~ 0.6MPa.
5. the method for a kind of fluidized bed olefin disproportionation propylene according to claim 1, is characterized in that weight space velocity is 4 ~ 8 hours
-1.
6. the method for a kind of fluidized bed olefin disproportionation propylene according to claim 1, is characterized in that with the consumption of weight parts Tungsten oxide 99.999 be 2 ~ 16 parts.
7. the method for a kind of fluidized bed olefin disproportionation propylene according to claim 6, is characterized in that with the consumption of weight parts Tungsten oxide 99.999 be 4 ~ 12 parts.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1373007A (en) * | 2001-02-28 | 2002-10-09 | 中国科学院大连化学物理研究所 | Catalyst for preparing propylene by dismutation reaction and its preparing process and application |
| CN1465434A (en) * | 2002-06-20 | 2004-01-07 | 中国科学院大连化学物理研究所 | Catalyst for reversal disproportionation preparation of propene from ethylene and butylene |
| CN101172926A (en) * | 2006-11-02 | 2008-05-07 | 中国石油化工股份有限公司 | Propylene yield increasing method |
| CN102464548A (en) * | 2010-11-17 | 2012-05-23 | 中国石油化工股份有限公司 | Method for preparing propylene by olefin disproportionation in fluidized bed |
-
2012
- 2012-10-25 CN CN201210412603.3A patent/CN103772108B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1373007A (en) * | 2001-02-28 | 2002-10-09 | 中国科学院大连化学物理研究所 | Catalyst for preparing propylene by dismutation reaction and its preparing process and application |
| CN1465434A (en) * | 2002-06-20 | 2004-01-07 | 中国科学院大连化学物理研究所 | Catalyst for reversal disproportionation preparation of propene from ethylene and butylene |
| CN101172926A (en) * | 2006-11-02 | 2008-05-07 | 中国石油化工股份有限公司 | Propylene yield increasing method |
| CN102464548A (en) * | 2010-11-17 | 2012-05-23 | 中国石油化工股份有限公司 | Method for preparing propylene by olefin disproportionation in fluidized bed |
Non-Patent Citations (1)
| Title |
|---|
| Effect of support nature on WO3/SiO2 structure and butene-1 metathesis;Yangdong Wang et al.,;《Applied Catalysis A: General》;20031231;第250卷;第25-37页 * |
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