CN105618064B - The preparation method of butylene oxidation-dehydrogenation catalyst - Google Patents
The preparation method of butylene oxidation-dehydrogenation catalyst Download PDFInfo
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Abstract
A kind of method prepared by butylene oxidation-dehydrogenation catalyst, two step plastic coprecipitation methods prepare catalyst, the first step to iron content, zinc, calcium series elements aqueous solution in just titrating ammonium hydroxide control system pH to 7.0 8.0 be added dropwise；Second step stops that ammonium hydroxide is added dropwise, and is continually fed into CO20.5~2 hour, maintenance system pH was constant, then adds sesbania powder, and mixing gained precipitation obtains butylene oxidation-dehydrogenation catalyst after ageing, washing, drying, roasting.
Description
Technical field
The present invention relates to catalyst more particularly to a kind of Fe-series catalyst for n-butene oxidative dehydrogenation butadiene and
Preparation method and use.
Background technology
Butadiene is the important monomer of synthetic rubber etc..Main production process uses naphtha steam cracking by-product butadiene
Extracting, this method is affected by oil price.Industrially the method for butane or butylene oxidation-dehydrogenation was once used to produce fourth two
Alkene.Since alkane is more stable, the general temperature of butane dehydrogenation technique is higher, and side reaction is more, 600 DEG C of typical reaction temperature, base
In the butadiene yield 65% of butane.Butylene is more active, and most typical butylene oxidation-dehydrogenation technique is Petro-Tex Oxo-D
Technique, butadiene selective is higher, and generally higher than 90%, side reaction and by-product are less.
It in conjunction with China's national situation, is influenced by factors such as emission reductions, natural gas is greatly developed as domestic fuel, annual to increase
Width is more than 10,000,000,000 sides, to squeeze market of refinery's C-4-fraction as liquefied gas as fuel significantly so that refinery's C-4-fraction
The condition for facing dull sale and price in easy can be sayed without economic benefit.Refinery's C-4-fraction utilizes its isobutyl in addition to etherificate
Outside alkene, also 70% C-4-fraction can not be utilized valuably.And C-4-fraction contains up to 50% butylene-after these ethers
1 and butene-2, the exactly good raw material of Oxidative Dehydrogenation of Butene into Butadiene.It is high using high-performance butylene oxidation-dehydrogenation catalyst
Butylene after effect trans-utilization ether in C-4-fraction, which produces butadiene, will have very significant economic benefit.
Oxidative Dehydrogenation of Butene into Butadiene reaction is since the sixties come out, by the catalyst institute of a variety of different systems
Catalysis, such as molybdenum system, tin system, antimony system and iron system.Industrial practice proves, in numerous catalyst systems, has Fe-series catalyst tool only
Have the advantages that reaction temperature is mild, catalytic activity is high, purpose product high selectivity.Thus in this technical process, either
Fluid bed or insulation fix bed uses Fe-series catalyst.Chinese patent CN1184705, CN1072110, CN1074631,
CN101674883 and CN1033013 etc. describes the preparation of the butadiene catalyst made by butylene oxidation dehydrogen based on ferrite
Method.The catalyst of which part patent once obtained commercial Application in China, was limited by catalyst at that time and technology level,
It is eliminated by naphtha pyrolysis by-product butadiene method.Although the above patent has obtained huge economic benefit in commercial Application,
The activity and selectivity of catalyst has also reached very high level, but today that environmental consciousness is increasingly serious, catalyst preparation
Zn content is excessively high in the waste water of generation, can not direct emission.The fluid bed butylene oxidation-dehydrogenation catalyst of commercial Application is at present
Zinc ferrite class catalyst, such as W-201 catalyst or R109 catalyst, which uses coprecipitation technology, with ammonia
Water is precipitating reagent, precipitates the nitrate of metal.It is well known that zinc can form zinc ammonium complex ion, under conditions of ammonium hydroxide surplus,
The zinc hydroxide of precipitation can dissolve.From the material balance and tailing water analysis explanation in catalyst preparation process, Zn is in best plastic
It when PH, cannot precipitate completely, Zn loses 25-30%, and utilization rate of zinc only has 70-75%.
In view of the more serious phenomenon of metal loss, the present invention proposes a kind of improvement catalyst preparation process, reach avoid or
Reduce the purpose that metallic zinc is lost in percentage.
Invention content
The object of the present invention is to provide a kind of methods prepared by the Oxydehydrogenation catalyst for avoiding or reducing metallic zinc loss.
The present invention provides a kind of method prepared by butylene oxidation-dehydrogenation catalyst, and two step plastic coprecipitation methods prepare catalysis
Agent, the first step to iron content, zinc, calcium series elements aqueous solution in just titrating be added dropwise ammonium hydroxide control system pH to 7.0-8.0；Second step
Stop that ammonium hydroxide is added dropwise, is continually fed into CO20.5~2 hour, maintenance system pH was constant, then adds sesbania powder, mixing gained precipitation warp
Butylene oxidation-dehydrogenation catalyst is obtained after crossing ageing, washing, drying, roasting.
Wherein, the ammonia concn is preferably 10-30%.
The system pH is preferably 7.6-7.9.
The sesbania powder dosage is preferably the 0.05-1% of total catalyst weight.
Wherein, Aging Temperature is preferably 60-90 DEG C, and digestion time is preferably 0.5-3h；More preferable scheme：Aging Temperature is
75-85 DEG C, digestion time 1-2h.
The present invention prepares catalyst by the coprecipitation method of two step plastics, and dropwise addition ammonium hydroxide is just being titrated by first step plastic
Ph to 7.0-8.0 is controlled, second step stops that ammonium hydroxide is added dropwise, and is passed through CO2, cause the zinc ammonium complex ion being lost in be converted into zinc carbonate,
It avoids or reduces zinc to be lost in into water, on this basis without changing spinel structure, maintains catalysagen activity.
Description of the drawings
Fig. 1：Catalyst crystalline phases structural analysis figure.
Specific implementation mode
It elaborates below to the embodiment of the present invention：The present embodiment is carried out lower based on the technical solution of the present invention
Implement, gives detailed embodiment and process, but protection scope of the present invention is not limited to following embodiments, following implementation
Test method without specific conditions in example, usually according to normal condition.
System pH：
In the present invention, system pH is not particularly limited, usually to iron content, zinc, calcium series elements aqueous solution in just dripping
Surely ammonium hydroxide control system pH to 7.0-8.0 is added dropwise, preferred embodiment system pH is 7.6-7.9；If ammonium hydroxide control system pH is added dropwise
Less than 7.0, then system acidity is excessive, and hydroxide precipitation can be caused incomplete, and the activity of catalyst is very low；However ammonium hydroxide is added dropwise
Control system pH is more than 8.0, then causes excessive zinc hydroxide to dissolve, be bound to cause the loss of zinc bigger.
It is passed through CO2Time：
In the present invention, to being passed through CO2Time is not particularly limited, and usual second step stops that ammonium hydroxide is added dropwise, and is continually fed into
CO20.5~2 hour, maintenance system pH was constant；If being passed through CO2Time is less than 0.5 hour, then since the time is too short, causes zinc
Conversion be not thorough；And it is passed through CO2Time is more than 2 hours, and the zinc of loss has been completely converted into precipitation, continues to be passed through CO2It can cause
The wasting of resources.
Ammonia concn：
In the present invention, ammonia concn is not particularly limited, usual ammonia concn is 10-30%, if ammonia concn
Less than 10%, then since ammonia concn is too small, then it can extend the sedimentation time；However if ammonia concn is more than 30%, due to
Concentration is excessive, it cannot be guaranteed that co-precipitation effect.
Sesbania powder dosage：
In the present invention, sesbania powder dosage is not particularly limited, usual sesbania powder dosage is total catalyst weight
0.05-1%, since sesbania powder dosage is insufficient, causes to be catalyzed if sesbania powder dosage is less than the 0.05% of total catalyst weight
Agent difficult forming；And sesbania powder dosage is more than the 1% of total catalyst weight, can reduce the intensity of catalyst.
Aging condition：
In the present invention, aging condition is not particularly limited, usual Aging Temperature is 60-90 DEG C, and digestion time is
0.5-3h；Preferred embodiment Aging Temperature is 75-85 DEG C, digestion time 1-2h；
If Aging Temperature is less than 60 DEG C, since temperature is too low, cause colloidal solid childlike；And Aging Temperature is higher than 90
DEG C, since Aging Temperature is excessively high, it may appear that destroy colloidal solid, reduce the activity of catalyst, have no other advantageous effects；
If digestion time causes colloidal solid too small less than 0.5h since digestion time is too short, subsequent filter effect is influenced
Fruit；And digestion time is more than 3h, destroys colloidal solid, influences the activity of catalyst, have no other beneficial effects.
Embodiment 1
Accurately weigh analytically pure Fe (NO3)3·9H2O 216.4g, analytically pure Zn (NO3)2·6H2O 71.2g, analysis
Pure Ca (NO3)2·6H2O 2.4g are added 1000ml deionized waters and are configured to mixed solution.Acquired solution with 10% ammonium hydroxide
Solution is precipitated, and solution ph is monitored with pH meter, until pH value is 7.6 stopping dropwise additions, first cemented into bundles, at this time to molten
Carbon dioxide is passed through with 600ml/min in liquid.Continue 1 hour, stopping is passed through carbon dioxide, then adds 1.8g sesbania powders, mixes
After good, gained precipitation is placed in 80 DEG C of constant temperature and is aged 1.0 hours.It is washed with deionized 4 times, each slurry 500ml.Waste water
Middle zinc is lost in 12.6%, utilization rate of zinc 87.6% in solid, 24 hours dry through 120 DEG C, is placed in 700 DEG C of roastings in Muffle furnace and lives
Change 10h, grinding screening takes 20-60 mesh, is packed into 10ml fixed bed evaluating apparatus and is evaluated, and the control of reaction process condition temperature exists
376 DEG C, oxygen alkene is than 0.70, and water alkene is than 14.8, reacted rear butene conversion 82.75%, selectivity 92.97%, yield
76.94%, specifically it is shown in Table 2.
Embodiment 2
Analytically pure Zn (NO are added after 54% nitric acid 540ml dissolvings completely in 75g iron powders3)2·6H2O56.8g, point
Analyse pure CaCl20.8g, Ca (OH)20.9g is added 1000ml deionized waters and is configured to mixed solution.Acquired solution is with 10%
Ammonia spirit is precipitated, with pH meter monitor solution ph, until pH value be 7.8 stop be added dropwise, first cemented into bundles, at this time
It is passed through 400ml/min into solution and continues 1 hour, stopping is passed through carbon dioxide, then adds 1.3g sesbania powders, after mixing, institute
It must precipitate and be placed in 80 DEG C of constant temperature and be aged 1.0 hours.It is washed with deionized 4 times, each slurry 500ml.Zinc stream in waste water
9.45% is lost, utilization rate of zinc 90.55% in solid is 24 hours dry through 120 DEG C, is placed in 700 DEG C of calcination activations in Muffle furnace
10h, grinding screening take 20-60 mesh, are packed into 10ml fixed bed evaluating apparatus and are evaluated, and the control of reaction process condition temperature exists
368 DEG C, oxygen alkene is than 0.68, and water alkene is than 14.8, reacted rear butene conversion 88.98%, selectivity 91.76%, yield
81.64%, specifically it is shown in Table 2.
Embodiment 3
Accurately weigh analytically pure Fe (NO3)3·9H2O 536.9g, analytically pure Zn (NO3)2·6H2O125.6g, analysis
Pure CaCl22g, Ca (OH)22g is added 2000ml deionized waters and is configured to mixed solution.Acquired solution is molten with 10% ammonium hydroxide
Liquid is precipitated, and solution ph is monitored with pH meter, until pH value is 7.9 stopping dropwise additions, first cemented into bundles, at this time to solution
It is inside passed through 400ml/min and continues 1 hour, stopping is passed through carbon dioxide, then adds 3g sesbania powders, and after mixing, gained precipitation is set
It is aged 1.0 hours in 85 DEG C of constant temperature.It is washed with deionized 4 times, each slurry 1000ml.Zinc is lost in waste water
7.45%, utilization rate of zinc 92.55% in solid.It is 24 hours dry through 120 DEG C, 700 DEG C of calcination activation 10h in Muffle furnace are placed in,
Grinding screening takes 20-60 mesh, is packed into 10ml fixed bed evaluating apparatus and is evaluated, and reaction process condition temperature is controlled at 364 DEG C,
Water alkene is than 14.8, and different oxygen alkene are than lower reaction result such as following table.
The different oxygen alkene of table 1 than evaluation result (360-380 DEG C of temperature)
Crystal phase structure analysis is carried out to obtained catalyst, sees attached drawing 1, shows that its primary structure is α-Fe2O3、Zn
Fe2O4, without apparent other object phase diffraction maximums.It is consistent substantially with former W-201 catalyst object phase diffraction maximum.ZnFe2O4 and α-
Fe2O3The ratio between peak intensity increases to 10.9, ZnFe2O4 crystal grains degree by the 6.4 of a step plastic and also increased, by 30.6nm
It improves to 38.7nm.
Embodiment 4
1615g iron powders, 1056gZnO are added after 54% nitric acid 11L dissolvings completely and analyze pure CaCl218g, Ca (OH)221g is added 22L deionized waters and is configured to mixed solution.Acquired solution is precipitated with 10% ammonia spirit, is supervised with pH meter
Solution ph is surveyed, until pH value is that 8.0 stoppings are added dropwise, first cemented into bundles is passed through 600ml/min into solution and continues at this time
0.5 hour, stopping was passed through carbon dioxide, then adds 28g sesbania powders, and after mixing, gained precipitation is placed in 90 DEG C of constant temperature ageings 0.5
Hour.It is washed with deionized 4 times, each slurry 8L.Zinc is lost in 6.36% in waste water, utilization rate of zinc in solid
93.64%, it is 24 hours dry through 120 DEG C, 700 DEG C of calcination activation 10h in Muffle furnace are placed in, grinding screening takes 20-60 mesh, is packed into
10ml fixed bed evaluating apparatus is evaluated, and reaction process condition temperature is controlled at 360-380 DEG C, and oxygen alkene is than 0.68, water alkene ratio
14.8, reacted rear butene conversion 87.9%, selectivity 85.39%, yield 75.05% is specifically shown in Table 2.
Embodiment 5
Analytically pure Zn (NO are added after 54% nitric acid 540ml dissolvings completely in 75g iron powders3)2·6H2O56.8g, point
Analyse pure CaCl20.8g, Ca (OH)20.9g is added 1000ml deionized waters and is configured to mixed solution.Acquired solution is with 10%
Ammonia spirit is precipitated, with pH meter monitor solution ph, until pH value be 7.4 stop be added dropwise, first cemented into bundles, at this time
It is passed through 400ml/min into solution and continues 2 hours, stopping is passed through carbon dioxide, then adds 1.3g sesbania powders, after mixing, institute
It must precipitate and be placed in 90 DEG C of constant temperature and be aged 0.5 hour.It is washed with deionized 4 times, each slurry 500ml.Zinc stream in waste water
13.45% is lost, utilization rate of zinc 86.55% in solid is 24 hours dry through 120 DEG C, is placed in 700 DEG C of calcination activations in Muffle furnace
10h, grinding screening take 20-60 mesh, are packed into 10ml fixed bed evaluating apparatus and are evaluated, and the control of reaction process condition temperature exists
368 DEG C, oxygen alkene is than 0.68, and water alkene is than 14.8, reacted rear butene conversion 72.49%, selectivity 81.16%, yield
58.83%, specifically it is shown in Table 2.
Embodiment 6
Analytically pure Zn (NO are added after 54% nitric acid 2800ml dissolvings completely in 350g iron powders3)2·6H2O322g, point
Analyse pure CaCl24g, Ca (OH)25g is added 5000ml deionized waters and is configured to mixed solution.Acquired solution with 10% ammonium hydroxide
Solution is precipitated, and solution ph is monitored with pH meter, until pH value is 7.0 stopping dropwise additions, first cemented into bundles, at this time to molten
It is passed through 600ml/min in liquid and continues 0.5 hour, stopping is passed through carbon dioxide, then adds 6.8g sesbania powders, after mixing, gained
Precipitation is placed in 75 DEG C of constant temperature and is aged 1.0 hours.It is washed with deionized 4 times, each slurry 1500ml.Zinc is lost in waste water
10.63%, utilization rate of zinc 89.37% in solid is 24 hours dry through 120 DEG C, is placed in 700 DEG C of calcination activation 10h in Muffle furnace,
Grinding screening takes 20-60 mesh, is packed into 10ml fixed bed evaluating apparatus and is evaluated, reaction process condition temperature is controlled in 370-
380 DEG C, oxygen alkene ratio 0.65-0.68, water alkene ratio 12-14, reacted rear butene conversion 56.27%, selectivity 72.35% is received
Rate 40.71%, is specifically shown in Table 2.
Embodiment 7
Accurately weigh analytically pure Fe (NO3)3·9H2O 216.4g, analytically pure Zn (NO3)2·6H2O 65.2g, analysis
Pure Ca (NO3)2·6H2O 2.4g are added 1000ml deionized waters and are configured to mixed solution.Acquired solution with 10% ammonium hydroxide
Solution is precipitated, and solution ph is monitored with pH meter, until pH value is 7.6 stopping dropwise additions, first cemented into bundles, at this time to molten
Carbon dioxide is passed through with 600ml/min in liquid.Continue 0.5 hour, stopping is passed through carbon dioxide, then adds 1.8g sesbania powders, mixes
After getting togather, gained precipitation is placed in 65 DEG C of constant temperature and is aged 3.0 hours.It is washed with deionized 4 times, each slurry 500ml.It is useless
Zinc is lost in 8.67% in water, utilization rate of zinc 91.33% in solid, 24 hours dry through 120 DEG C, is placed in 700 DEG C of roastings in Muffle furnace
Activation 10h is burnt, grinding screening takes 20-60 mesh, is packed into 10ml fixed bed evaluating apparatus and is evaluated, reaction process condition temperature control
System is at 376 DEG C, and oxygen alkene is than 0.70, and water alkene is than 14.8%, reacted rear butene conversion 85.75%, selectivity 91.47, yield
78.43%, specifically it is shown in Table 2.
Embodiment 8
Accurately weigh analytically pure Fe (NO3)3·9H2O 216.4g, analytically pure Zn (NO3)2·6H2O71.2g, analysis
Pure Ca (NO3)2·6H2O 2.4g are added 1000ml deionized waters and are configured to mixed solution.Acquired solution with 10% ammonium hydroxide
Solution is precipitated, and solution ph is monitored with pH meter, until pH value is 8.5 to stop being added dropwise, then is added 1.8g sesbania powders, is mixed
Afterwards, gained precipitation is placed in 80 DEG C of constant temperature and is aged 1.0 hours.It is washed with deionized 4 times, each slurry 500ml.In waste water
Zinc is lost in 28.6%, utilization rate of zinc 71.4% in solid, 24 hours dry through 120 DEG C, is placed in 700 DEG C of calcination activations in Muffle furnace
10h, grinding screening take 20-60 mesh, are packed into 10ml fixed bed evaluating apparatus and are evaluated, and the control of reaction process condition temperature exists
376 DEG C, oxygen alkene is than 0.70, and water alkene is than 14.8, reacted rear butene conversion 80.13%, selectivity 91.52%, yield
73.33%, specifically it is shown in Table 2.
Embodiment 9
Accurately weigh analytically pure Fe (NO3)3·9H2O 216.4g, analytically pure Zn (NO3)2·6H2O 71.2g, analysis
Pure Ca (NO3)2·6H2O 2.4g are added 1000ml deionized waters and are configured to mixed solution.Acquired solution with 10% ammonium hydroxide
Solution is precipitated, and solution ph is monitored with pH meter, until pH value is 8.2 to stop being added dropwise, then is added 1.8g sesbania powders, is mixed
Afterwards, gained precipitation is placed in 80 DEG C of constant temperature and is aged 1.0 hours.It is washed with deionized 4 times, each slurry 500ml.In waste water
Zinc is lost in 30.06%, utilization rate of zinc 69.94% in solid, 24 hours dry through 120 DEG C, is placed in 700 DEG C of roastings in Muffle furnace and lives
Change 10h, grinding screening takes 20-60 mesh, is packed into 10ml fixed bed evaluating apparatus and is evaluated, and the control of reaction process condition temperature exists
376 DEG C, oxygen alkene is than 0.70, and water alkene is than 14.8, reacted rear butene conversion 81.38%, selectivity 90.58%, yield
73.71%, specifically it is shown in Table 2.
2 each embodiment performance test of table
| Embodiment | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 |
| Terminal pH | 7.6 | 7.8 | 7.9 | 8.0 | 7.4 | 7.0 | 7.6 | 8.5 | 8.2 |
| Zinc loss/% | 12.6 | 9.45 | 7.45 | 6.36 | 13.45 | 10.63 | 8.67 | 28.6 | 30.06 |
| Conversion ratio/% | 82.75 | 76.49 | 94.52 | 87.9 | 72.49 | 56.27 | 85.75 | 80.13 | 81.38 |
| Selectivity/% | 92.97 | 89.16 | 91.36 | 85.39 | 81.16 | 72.35 | 91.47 | 91.52 | 90.58 |
| Yield/% | 76.94 | 68.20 | 86.36 | 75.05 | 58.83 | 40.71 | 78.43 | 73.33 | 73.71 |
Claims (7)
1. a kind of method prepared by butylene oxidation-dehydrogenation catalyst, it is characterised in that：Two step plastic coprecipitation methods prepare catalysis
Agent, the first step to iron content, zinc, calcium series elements aqueous solution in just titrating be added dropwise ammonium hydroxide control system pH to 7.6-7.9；Second step
Stop that ammonium hydroxide is added dropwise, is continually fed into CO20.5~2 hour, maintenance system pH was constant, then adds sesbania powder, mixing gained precipitation warp
Butylene oxidation-dehydrogenation catalyst is obtained after crossing ageing, washing, drying, roasting.
2. method prepared by butylene oxidation-dehydrogenation catalyst according to claim 1, it is characterised in that：The ammonia concn
For 10-30%.
3. method prepared by butylene oxidation-dehydrogenation catalyst according to claim 1 or 2, it is characterised in that：The sesbania
Powder dosage is the 0.05-1% of total catalyst weight.
4. method prepared by butylene oxidation-dehydrogenation catalyst according to claim 1 or 2, it is characterised in that：Aging Temperature
It is 60-90 DEG C, digestion time 0.5-3h.
5. method prepared by butylene oxidation-dehydrogenation catalyst according to claim 3, it is characterised in that：Aging Temperature is
60-90 DEG C, digestion time 0.5-3h.
6. method prepared by butylene oxidation-dehydrogenation catalyst according to claim 4, it is characterised in that：Aging Temperature is
75-85 DEG C, digestion time 1-2h.
7. method prepared by butylene oxidation-dehydrogenation catalyst according to claim 5, it is characterised in that：Aging Temperature is
75-85 DEG C, digestion time 1-2h.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1072110A (en) * | 1991-11-01 | 1993-05-19 | 中国科学院兰州化学物理研究所 | Butylene oxidation dehydrogenation catalyst for fluidized bed |
| CN102716754A (en) * | 2012-07-12 | 2012-10-10 | 上海碧科清洁能源技术有限公司 | Catalyst for preparing butadiene by oxidative dehydrogenation of butene in fluidized bed reactor and preparation method and application thereof |
| CN103657680A (en) * | 2012-09-26 | 2014-03-26 | 上海华谊丙烯酸有限公司 | Ferrate catalyst, preparation method and application of ferrate catalyst |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1072110A (en) * | 1991-11-01 | 1993-05-19 | 中国科学院兰州化学物理研究所 | Butylene oxidation dehydrogenation catalyst for fluidized bed |
| CN102716754A (en) * | 2012-07-12 | 2012-10-10 | 上海碧科清洁能源技术有限公司 | Catalyst for preparing butadiene by oxidative dehydrogenation of butene in fluidized bed reactor and preparation method and application thereof |
| CN103657680A (en) * | 2012-09-26 | 2014-03-26 | 上海华谊丙烯酸有限公司 | Ferrate catalyst, preparation method and application of ferrate catalyst |
Non-Patent Citations (1)
| Title |
|---|
| 碳酸锌的沉淀及分解制备活性氧化锌;周新木等;《南昌大学学报（工科版）》;20091231;第31卷(第4期);摘要，第2.1节、第2.2节 * |
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