CN103769127B - Ammoxidation method to manufacturing unsaturated nitrile fluid-bed catalyst - Google Patents

Ammoxidation method to manufacturing unsaturated nitrile fluid-bed catalyst Download PDF

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CN103769127B
CN103769127B CN201210393207.0A CN201210393207A CN103769127B CN 103769127 B CN103769127 B CN 103769127B CN 201210393207 A CN201210393207 A CN 201210393207A CN 103769127 B CN103769127 B CN 103769127B
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catalyst
unsaturated nitrile
low
acrylonitrile
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CN103769127A (en
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吴粮华
姜家乐
张顺海
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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    • Y02P20/00—Technologies relating to chemical industry
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    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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Abstract

The present invention relates to a kind of ammoxidation method to manufacturing unsaturated nitrile fluid-bed catalyst, mainly in solution prior art, the ability of acrylonitrile catalyst storage oxygen and release oxygen is low, specific surface is low, and be easy to sintering at the reaction temperatures, cause propylene conversion low, acrylonitrile selectivity is low, and decline fast, cause the problem that acrylonitrile yield is low.The present invention is carrier by adopting with Ludox, the active constituent containing following general formula represents: Mo 12bi afe bni cx dy ek fz gq ho x, the technical scheme that wherein Z and Q is prepared into catalyst more first form solid solution under precipitating reagent effect after solves this problem preferably, can be used in the industrial production of ammoxidating propylene to prepare acrylonitrile.

Description

Ammoxidation method to manufacturing unsaturated nitrile fluid-bed catalyst
Technical field
The present invention relates to a kind of fluid catalyst of prepared by ammoxidation unsaturated nitrile, particularly about the fluid catalyst of propylene, butylene preparing acrylonitrile by ammoxidation, butene nitrile.
Background technology
The prepared by ammoxidation of alkene is developed sixties last century in last century by BP company for α, beta unsaturated nitrile technique, and the core technology of this technique is the catalyst using a kind of active component to contain Mo, Bi.Through constantly improving, current Mo-Bi series catalysts is very ripe, is industrially widely used by preparing acrylonitrile by allylamine oxidation technique.The improvement of catalyst in the past is mainly carried out from the activity of catalyst and stability aspect by the design of catalyst formulation, and as added transition metal to improve activity in active constituent, the list increasing product is received; Add rare earth element and improve redox ability; Add the elements such as Na, P to improve the wearability of catalyst; Add the elements such as Fe, Co, Ni to suppress the distillation of Mo, improve stability of catalyst etc.
Patent CN99119905.7, CN99119906.5, CN97106771.6 and CN96101529.2 all describe the Mo-Bi catalyst for propylene, isobutene ammonia oxidizing unsaturated nitrile catalyst of improvement, the advantage of these catalyst has good oxidation-reduction stability and reaction yield preferably, reacting ammonia than empty than and reaction temperature lower.
Patent CN01113194.2, CN01113193.4 and CN01113192.6 describe and in catalyst preparation process, to get method that part metals and organic ligand, chelating agent or surfactant prepared separately to improve catalyst at low ammonia than the performance under reaction condition.
Patent CN03151170.8 and CN03151169.4 describes in catalyst preparation process, and the grain diameter adding 2 ~ 25% in carrier starting material Ludox is that the solid silica of 5 ~ 100 nanometers is to improve catalyst performance.
Above patented technology is to the conversion ratio improving catalyst, and reduce the discharge of ammonia ratio and then minimizing amine wastewater of sulphuric acid in course of reaction, there has been certain effect the aspects such as the life-span of extending catalyst; But patent report up to now, all there is acrylonitrile catalyst storage oxygen with the ability discharging oxygen is low, specific surface is low, and be easy to sintering at the reaction temperatures, cause propylene conversion low, acrylonitrile selectivity is low, and declines fast, causes the problem that acrylonitrile yield is low.
Summary of the invention
Technical problem to be solved by this invention there is acrylonitrile catalyst storage oxygen in prior art with the ability discharging oxygen is low, specific surface is low, and be easy to sintering at the reaction temperatures, cause propylene conversion low, acrylonitrile selectivity is low, and decline fast, cause the problem that acrylonitrile yield is low, a kind of new unsaturated nitrile fluid catalyst prepared by ammoxidation is provided.This catalyst has the ability, specific surface and the anti-caking power that effectively improve catalyst storage oxygen and release oxygen, for the reaction of prepared by ammoxidation unsaturated nitrile, and the advantage that acrylonitrile yield is high.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of ammoxidation method to manufacturing unsaturated nitrile fluid-bed catalyst, take Ludox as carrier, the active component containing following general formula represents:
Mo 12bi afe bni cx dy ek fz gq ho x, wherein Z and Q is prepared into catalyst after first forming solid solution again;
X is at least one be selected from Mg, Co, Ca, Be, Cu, Zn, Pb, Mn or Te;
Y is at least one be selected from Rb, Li or Cs;
Z is at least one be selected from La, Ce, Pr, Nd or Sm;
Q is at least one be selected from Ti or Zr;
The span of a is 0.1 ~ 6.0;
The span of b is 0.1 ~ 10.0;
The span of c is 0.1 ~ 10.0;
The span of d is 0.1 ~ 10.0;
The span of e is >0 ~ 0.5;
The span of f is >0 ~ 0.2;
The span of g is 0.1 ~ 3;
The span of h is 0.1 ~ 1.0;
The span of g/h ratio is 0.05 ~ 20.0;
X is for meeting the oxygen atom sum needed for other element valence, and the consumption of carrier is 30 ~ 70% of catalyst weight.
In technique scheme, the span of g/h ratio is 0.1 ~ 10.0, and optimum valuing range is 1 ~ 5.The consumption preferable range of carrier is 40 ~ 60% of catalyst weight.The calcination activation temperature preferable range of catalyst is 550 ~ 640 DEG C; Calcination activation time preferable range is 0.5 ~ 2 hour.X is preferred version is at least one be selected from Mg, Co, Ca or Mn, and more preferably scheme is at least one be selected from Mg or Mn.Q preferred version is for being selected from Ti and Zr.The value preferable range of e is 0.01 ~ 0.3.The value preferable range of f is 0.01 ~ 0.15.
The coprecipitation preparation that catalyst can be familiar with those skilled in the art.The starting material of required metallic element is corresponding water soluble salt, slurry is made with Ludox carrier coprecipitation, the aging rear spray drying granulation of slurry, then high-temperature roasting obtains finished catalyst, calcination activation temperature preferable range is 550 ~ 640 DEG C, and calcination activation time preferable range is 0.5 ~ 2 hour.
In the following embodiment provided, to the investigation appreciation condition of catalyst be:
Reactor: fluidized-bed reactor, internal diameter 38 millimeters
Catalyst filling amount: 550 grams
Reactor top pressure: 0.084MPa (gauge pressure)
Reaction temperature: 430 DEG C
Reaction time: 4 hours
Raw material ratio: propylene/ammonia/air=1/1.1/9.5,
WWH:0.06 hour -1
Product 0 DEG C of diluted acid absorbs, with gas-chromatography and chemical analysis binding analysis product.And calculate Carbon balance, be valid data when Carbon balance is at (95 ~ 105) %.
Propylene conversion, acrylonitrile yield and be optionally defined as:
Unreacting propylene C molal quantity
Propylene conversion (%)=1- × 100%
All product C molal quantitys (comprising unreacting propylene)
Generate acrylonitrile C molal quantity
Single-pass yield of acrylonitrile (%)= × 100%
All product C molal quantitys (comprising unreacting propylene)
Single-pass yield of acrylonitrile
Acrylonitrile selectivity (%)= × 100%
Propylene conversion
The present invention is by first forming solid solution at acrylonitrile catalyst formula rare earth elements with high price component Ti, Zr, then catalyst is made, because rare-earth cation and the notable difference of high price component Ti, Zr cation radius cause distortion of lattice and blemish to significantly improve, promote that the oxidation one of body phase oxygen is reduced, cause the ability of high storage and release oxygen, catalyst specific surface increases, thus enhancing redox property, increase the selective oxidation reaction of propylene and Lattice Oxygen, and then also significantly increasing acrylonitrile selectivity, acrylonitrile yield significantly improves.As shown in table 2 result: the oxygen storage capacity of catalyst is increased to about 200 ~ 400 μm of ol/g of embodiment by 92 μm of ol/g of comparative example 1, rising scale about 3 ~ 5 times, put oxygen amount is increased to embodiment about 200 μm of ol/g by 58 μm of ol/g of comparative example 1, rising scale about 3 ~ 4 times, specific surface is by the 31m of comparative example 1 2/ g is increased to the about 40 ~ 50m of embodiment 2/ g, Be very effective; Acrylonitrile selectivity is increased to about 86% of embodiment by 81.5% of comparative example 1, and propylene conversion is increased to more than 99% of embodiment by 98.5% of comparative example 1, and single-pass yield of acrylonitrile is then increased to by 80.3% and is up to 86.7%, achieves good technique effect.
Below by embodiment, the present invention is further elaborated.
Detailed description of the invention
[comparative example 1]
By the Ludox of 1400 gram 40% (weight), stir 0.5 hour, obtain material A.
By 441.4 grams of (NH 4) 6mo 7o 244H 2o joins in the warm water of 330 grams 70 DEG C, stirs and makes its whole dissolving obtain material B, added fast in the B of strong stirring by A, obtain material C.
By 213.1 grams of Fe (NO 3) 39H 2o adds in 70 DEG C of hot water of 150 grams, adds 201.8 grams of Bi (NO after stirring and dissolving again 3) 35H 2o, 274.8 grams of Ni (NO 3) 36H 2o, 96.3 grams of Mg (NO 3) 36H 2o, 72.5 grams of La (NO 3) 33H 2o, 18.6 grams of Sm (NO 3) 33H 2o, 9.0 grams of Zr (NO 3) 45H 2material D is made after O stirring and dissolving.
1.1 grams of KNO are added in 20 grams of water 3, 0.9 gram of NaNO 3with 2.0 grams of CsNO 3added after dissolving in material D and formed material E.
Material E is dripped under fast stirring in material C, form catalyst pulp.In 70 DEG C of spraying dry after aging 3 hours, by the roasting 3 hours at 580 DEG C in rotary calciner of the particle of gained, obtain finished catalyst.
[embodiment 1 ~ 15]
According to the preparation process that comparative example 1 is identical, according to table 1 catalyst composition Kaolinite Preparation of Catalyst, difference is only that first with at high price component Ti, Zr, by ammoniacal liquor co-precipitation, oven dry, roasting, form solid solution, are then ground to less than 20 microns and add rare earth element.Catalyst is investigated by above-mentioned investigation appreciation condition, and Activity evaluation, catalyst storage oxygen, release oxygen amount and surface analysis the results are shown in Table 2.
Table 1
Catalyst forms
Comparative example 1 Mo 12Bi 2.0Fe 2.5Ni 4.5Mg 1.8La 0.8Sm 0.2Zr 0.1K 0.05Cs 0.05Na 0.05+50%SiO 2
Embodiment 1 (Mo 12Bi 2.0Fe 2.5Ni 4.5Mg 1.8K 0.05Cs 0.05Na 0.05)(La 0.8Sm 0.2Zr 0.1)+50%Si O 2
Embodiment 2 (Mo 12Bi 0.4Fe 2.2Ni 5.4Mg 2.4K 0.1Rb 0.08)(Nd 0.2Zr 0.05)+46%SiO 2
Embodiment 3 (Mo 12Bi 0.7Fe 1.5Ni 6.8Mg 1.6K 0.1Cs 0.05)(La 0.3Nd 0.2Sm 0.6Zr 0.05)+50%SiO 2
Embodiment 4 (Mo 12Bi 1.4Fe 1.6Ni 4.7Co 3.0K 0.02Cs 0.09)(La 0.5 Pr 0.1Sm 0.2Nd 0.1Ti 0.05Zr 0.05)+52%SiO 2
Embodiment 5 (Mo 12Bi 0.5Fe 3.2Ni 3.0Mg 1.8K 0.05Cs 0.05)(Sm 0.2Ti 0.2Zr 0.2)+50%SiO 2
Embodiment 6 (Mo 12Bi 0.2Fe 2.8Ni 5.3Mn 0.7K 0.11Cs 0.05)(Ce 0.4La 0.1Pr 0.1Sm 0.2Nd 0.2Ti 0.05)+50%SiO 2
Embodiment 7 (Mo 12Bi 0.9Fe 3.2Ni 5.5Mg 2.8K 0.12Cs 0.13) (Pr 0.1Ti 0.05Zr 0.05)+52% SiO 2
Embodiment 8 (Mo 12Bi 0.5Fe 2.2Ni 5.6K 0.15Cs 0.1Li 0.05)(Ce 0.3Nd 0.2Ti 0.2)+47%SiO 2
Embodiment 9 (Mo 12Bi 0.2Fe 2.8Ni 4.1Mg 3.5K 0.05Cs 0.1)(Pr 0.1Nd 0.2Zr 0.03Ti 0.2)+48%SiO 2
Embodiment 10 (Mo 12Bi 1.3Fe 2.0Ni 6.5Mg 1.8K 0.08Rb 0.05Cs 0.05)(Ce 0.1Nd 0.02Zr 0.3Ti 0.5)+50%SiO 2
Embodiment 11 (Mo 12Bi 1.2Fe 3.5Ni 2.7Mg 2.5K 0.12Cs 0.07Li 0.03)(La 0.1Pr 0.1Sm 0.2Ti 0.08)+51%SiO 2
Embodiment 12 (Mo 12Bi 0.6Fe 1.2Ni 6.5Mg 1.5K 0.15Cs 0.05)(Sm 1.4Ti 0.05)+50%SiO 2
Embodiment 13 (Mo 12Bi 0.2Fe 1.4Ni 6.3Mn 0.5Ca 0.2K 0.11Cs 0.09)(Sm 0.02Pr 0.1Ti 0.05Zr 0.05)+50%SiO 2
Embodiment 14 (Mo 12Bi 0.6Fe 2.5Ni 4.5Mg 0.8K 0.06Rb 0.07Cs 0.08)(Ce 0.02La 0.01Sm 0.02Ti 0.8)+50%SiO 2
Embodiment 15 (Mo 12Bi 0.4Fe 3..2Ni 1.5 Mg 2.8K 0.14Cs 0.12)(Ce 0.3La 0.1 Pr 0.1Nd 0.2Zr 0.02)+51%SiO 2
Table 2

Claims (9)

1. an ammoxidation method to manufacturing unsaturated nitrile fluid-bed catalyst take Ludox as carrier, the active component containing following general formula represents:
Mo 12bi afe bni cx dy ek fz gq ho x, wherein Z and Q is prepared into catalyst after first forming solid solution again;
X is at least one be selected from Mg, Co, Ca, Be, Cu, Zn, Pb, Mn or Te;
Y is at least one be selected from Rb, Li or Cs;
Z is at least one be selected from La, Ce, Pr, Nd or Sm;
Q is at least one be selected from Ti or Zr;
The span of a is 0.1 ~ 6.0;
The span of b is 0.1 ~ 10.0;
The span of c is 0.1 ~ 10.0;
The span of d is 0.1 ~ 10.0;
The span of e is 0 ~ 0.5, and non-vanishing;
The span of f is 0 ~ 0.2, and non-vanishing;
The span of g is 0.1 ~ 3;
The span of h is 0.1 ~ 1.0;
The span of g/h ratio is 0.05 ~ 20.0;
X is for meeting the oxygen atom sum needed for other element valence, and the consumption of carrier is 30 ~ 70% of catalyst weight.
2. ammoxidation method to manufacturing unsaturated nitrile fluid-bed catalyst according to claim 1, is characterized in that the span of g/h ratio is 0.1 ~ 10.0.
3. ammoxidation method to manufacturing unsaturated nitrile fluid-bed catalyst according to claim 2, is characterized in that the span of g/h ratio is 1 ~ 5.
4. ammoxidation method to manufacturing unsaturated nitrile fluid-bed catalyst according to claim 1, is characterized in that the consumption of carrier is catalyst weight 40 ~ 60%.
5. ammoxidation method to manufacturing unsaturated nitrile fluid-bed catalyst according to claim 1, is characterized in that X is at least one be selected from Mg, Co, Ca or Mn.
6. ammoxidation method to manufacturing unsaturated nitrile fluid-bed catalyst according to claim 5, is characterized in that X is at least one be selected from Mg or Mn.
7. ammoxidation method to manufacturing unsaturated nitrile fluid-bed catalyst according to claim 1, is characterized in that Q is selected from Ti and Zr.
8. ammoxidation method to manufacturing unsaturated nitrile fluid-bed catalyst according to claim 1, is characterized in that the span of e is 0.01 ~ 0.3.
9. ammoxidation method to manufacturing unsaturated nitrile fluid-bed catalyst according to claim 1, is characterized in that the span of f is 0.01 ~ 0.15.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4760159A (en) * 1987-03-13 1988-07-26 The Standard Oil Company Method for ammoxidation of paraffins and catalyst therefor
CN1172472A (en) * 1995-01-31 1998-02-04 旭化成工业株式会社 Process for producing unsaturated nitriles
CN101797510A (en) * 2010-04-02 2010-08-11 华东理工大学 Catalyst containing rare earth for ammoxidation of alkane
CN102371156A (en) * 2010-08-23 2012-03-14 中国石油化工股份有限公司 Unsaturated nitrile fluidized bed catalyst prepared by ammoxidation and its preparation method

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4760159A (en) * 1987-03-13 1988-07-26 The Standard Oil Company Method for ammoxidation of paraffins and catalyst therefor
CN1172472A (en) * 1995-01-31 1998-02-04 旭化成工业株式会社 Process for producing unsaturated nitriles
CN101797510A (en) * 2010-04-02 2010-08-11 华东理工大学 Catalyst containing rare earth for ammoxidation of alkane
CN102371156A (en) * 2010-08-23 2012-03-14 中国石油化工股份有限公司 Unsaturated nitrile fluidized bed catalyst prepared by ammoxidation and its preparation method

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