CN1219532A - Catalyst for propylene and isobutylene ammoxidation fluidized bed - Google Patents

Catalyst for propylene and isobutylene ammoxidation fluidized bed Download PDF

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CN1219532A
CN1219532A CN97106771A CN97106771A CN1219532A CN 1219532 A CN1219532 A CN 1219532A CN 97106771 A CN97106771 A CN 97106771A CN 97106771 A CN97106771 A CN 97106771A CN 1219532 A CN1219532 A CN 1219532A
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mixture
catalyzer
propylene
catalyst
acrylonitrile
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CN1055285C (en
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姜家乐
杨斌
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China Petroleum and Chemical Corp
Sinopec Shanghai Petrochemical Co Ltd
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Sinopec Shanghai Petrochemical Co Ltd
China Petrochemical Corp
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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Abstract

A fluidized-bed catalyst for preparing acrylonitrile or methyl acrylonitrile by the oxidization of propylene or isocrotyl ammonia contains the active components expressed by KaMobBicFedNieXfYgZhQiOx, where X is the mixture of one or more from Mg, Co, Ca and Be, Y is the mixture of one or more from La, Ce and Sm, Z is the mixture of one or more from Rb, Cs and Na, Q is the mixture of one or more from B, W, P and V, a-i are the atom number of correspondent elements and x is the oxygen atom number for meeting the chemical valence of other elements. Its advantages are high transformation rate of olefin and high selectivity to acrylonitrile or methy acrylonitrile.

Description

Propylene, isobutylene ammoxidation fluidized bed catalyzer
The present invention relates to be produced by olefin ammoxidation the catalyzer of unsaturated nitrile, its active constituent contains multiple metal oxides such as molybdenum, bismuth, iron.
The Mo-Bi catalyzer is to be used for the ripe and commonly used catalyzer of reaction that alkene is produced unsaturated nitrile (as producing vinyl cyanide or methacrylonitrile by propylene, isobutene ammonia oxidizing), and has constantly had patent to release new improvement prescription since being born.As in active constituent, adding transition metal or rare earth element, increase the single of product and receive to improve activity; Add alkali metals such as Na, K to improve the wear resistance of catalyzer; Add elements such as Fe, Co, Ni to suppress the volatilization of Mo, improve stability of catalyzer or the like.Patent CN 94191775.4 has introduced a kind of improved Mo-Bi catalyzer, its advantage is to produce vinyl cyanide or methacrylonitrile by high productivity, can make also that oxidative ammonolysis is stable to carry out even prolong the reaction times in process of production, thereby the reduction of vinyl cyanide or methacrylonitrile productive rate is very little during making.
The purpose of this invention is to provide a kind of new Mo-Bi catalyzer, compare, except that still possessing its advantage that has, also have higher propylene conversion and higher vinyl cyanide or methacrylonitrile once through yield simultaneously with the similar catalyst of above-mentioned documents introduction.
Mo-Bi catalyzer provided by the invention contains molybdenum, bismuth, iron, nickel, potassium, and randomly contain one or more metal oxides in magnesium, cobalt, calcium, beryllium, lanthanum, cerium, samarium, rubidium, caesium, sodium, boron, tungsten, vanadium and the phosphorus, its active constituent that contains is by following general formula:
K a??Mo b??Bi c??Fe d??Ni e??X f??Y g??Z h??Q i??O x
Wherein:
X is one or more the mixture among Mg, Co, Ca, the Be;
Y is one or more the mixture among La, Ce, the Sm;
Z is one or more the mixture among Rb, Cs, the Na;
Q is one or more the mixture among B, W, P, the V;
A=0～0.5; B=11～13; C, d, e, f, g=0.2～10; H, i=0～2; X satisfies the required Sauerstoffatom sum of other element valence;
The used carrier of catalyzer is silicon-dioxide or aluminum oxide, and its content is (40～60) % (w.t.) of catalyzer total amount.
Wherein, X is preferably Mg or Co or its mixture; Y is preferably La or Ce or its mixture; Z is preferably Rb or Cs or its mixture; Q is preferably W or V or its mixture.Carrier is preferably selected silicon-dioxide for use.The Slurry mixing preparation that catalyzer can be familiar with those skilled in the art, the raw material that is used to prepare the catalyzer each component is generally nitrate or other water-soluble salt or acids, so that each component mixes.
Compared with the prior art, catalyzer provided by the invention has redox ability preferably, under the wideer reaction conditions of scope, good oxidation-reduction stability is arranged, still can obtain higher product list thereby air that can be lower/alkene compares receives, under the prerequisite of the higher olefin conversion of maintenance, the selectivity of vinyl cyanide or methacrylonitrile has raising more significantly.In addition, catalyzer provided by the invention has also that temperature of reaction is low, the catalyst cupport advantages of higher.
To further describe details of the present invention by embodiment below, can find out positively effect of the present invention significantly by the evaluating data of embodiment.
In the following embodiment that provides, the actual conditions of catalyzer being investigated evaluation is: reactor: fluidized-bed reactor, internal diameter 38mm catalyst filling amount: 550g reactor top pressure: 0.84kg/cm 2(gauge pressure) temperature of reaction: 425 ℃ of reaction times: 4 hours raw material ratio: propylene/ammonia/air=1/1.15/9.5 (mol ratio) WWH:0.06
Reaction product absorbs with 0 ℃ of acid solution and water, with gas-chromatography and chemical analysis binding analysis product.And the calculating carbon balance, when carbon balance is valid data during at (95～105) %.
Propylene conversion, acrylonitrile yield and optionally be defined as:
Figure A9710677100041
Figure A9710677100042
Figure A9710677100043
Embodiment 1.
With 430.4g (NH 4) 6Mo 7O 244H 2O joins in the warm water of 70 ℃ of 330g, stirs and makes its whole dissolvings, adds the silicon sol of 1250g40% again, makes material A.
With 166g Fe (NO 3) 39H 2O adds in 70 ℃ of hot water of 40g, adds 55.8gBi (NO after the stirring and dissolving again 3) 35H 2O, 298.2gNi (NO 3) 36H 2O, 104.5gMg (NO 3) 36H 2O, 35.5gLa (NO 3) 311H 2O makes material B after the stirring and dissolving.
In 20g water, add 1.85gKNO 3And 1.78gRbNO 3, will form material C among its adding material B after the dissolving.
Material C is being dripped in material A under stirring fast, in 70 ℃ of spraying dryings after aging 3 hours, with the particle of gained in rotary calciner in 580 ℃ of following roastings 3 hours, finished catalyst.Embodiment 2～10
The Preparation of catalysts method only adopts corresponding different starting material with embodiment 1.
The starting material and the corresponding consumption of embodiment 1～10 preparation catalyzer are listed in table 1, and the composition of each catalyst activity component sees Table 2.
Finished catalyst is investigated by above-mentioned investigation appreciation condition, and it the results are shown in Table 3.
Table 1. (unit: gram)
(NH 4) 6Mo 7O 24 ?Bi(NO 3) 3?·5H 2O ?Fe(NO 3) 3·9H 2O ?Ni(NO 3) 2·6H 2O ?Mg(NO 3) 2·6H 2O Co(NO 3) 2·6H 2O ?La(NO 3) 3·nH 2O ?Ce(NO 3) 3·6H 2O ?KNO 3 ?RbNO 3 Cs?NO 3 NaNO 3 ?H 7P(N 2O 7) 6·nH 2O ?HBO 3 ?NH 4VO 3
Embodiment 1 embodiment 2 embodiment 3 embodiment 4 embodiment 5 embodiment 6 embodiment 7 embodiment 8 embodiment 9 embodiment 10 ?430.4 ?401.7 ?423.2 ?423.2 ?430.4 ?430.4 ?412.5 ?412.5 ?423.2 ?405.3 55.8 45.6 60.9 40.6 40.6 40.6 40.6 50.8 50.8 45.6 166.0 166.0 132.8 124.5 166.0 132.8 132.8 157.7 166.0 132.8 ?298.2 ?310.1 ?334.0 ?357.8 ?310.1 ?322.7 ?381.7 ?310.1 ?304.1 ?339.9 ?104.5 ?104.5 ?104.5 ?94.1 ???- ???- ???- ???- ???- ???- ????- ????- ?135.3 ?117.7 ?82.4 ?117.7 ?117.7 ?129.5 ?35.5 ?26.6 ?44.4 ?35.5 ???- ?4.40 ?35.5 ???- ?35.5 ?35.5 ???- ???- ???- ?35.5 ?31.0 ?43.9 ???- ???- ?1.85 ?1.85 ?1.44 ?1.64 ?1.64 ?1.44 ?1.64 ?1.64 ?1.44 ?1.85 ?1.78 ?1.78 ??- ??- ?2.08 ??- ?1.78 ?2.08 ???- ?1.78 ??- ??- ??- ?2.37 ?2.37 ??- ??- ?2.37 ??- ????- ????- ???0.87 ????- ????- ????- ????- ????- ????- ????- ?????- ????24.5 ????9.8 ?????- ?????- ?????- ????24.5 ????14.7 ??????- ????19.6 ?????- ?????- ????6.0 ?????- ?????- ????9.0 ?????- ?????- ????6.0 ????9.0 ?????- ????7.1 ?????- ????4.7 ?????- ?????- ?????- ????4.7 ????4.7 ????7.1
Table 2.
Embodiment 1 embodiment 2 embodiment 3 embodiment 4 embodiment 5 embodiment 6 embodiment 7 embodiment 8 embodiment 9 embodiment 10 ?K 0.09Mo 12Bi 0.55Fe 2Ni 5Mg 2La 0.4Rb 0.06O x?K 0.09Mo 11.2Bi 0.45Fe 2Ni 5.2Mg 2La 0.3Rb 0.06W 0.5V 0.3P 0.04O x?K 0.07Mo 11.8Bi 0.6Fe 1.6Ni 5.6Mg 2La 0.5Na 0.05W 0.2B 0.2P 0.016O x?K 0.08Mo 11.8Bi 0.4Fe 15Ni 6Mg 1.8La 0.4Cs 0.06V 0.2O x?K 0.08Mo 12Bi 0.4Fe 2Ni 5Co 2.3Ce 0.4Rb 0.07O x?K 0.07Mo 12Bi 0.4Fe 1.6Ni 5.4Co 2Ce 0.35La 0.05Cs 0.06B 0.3O x?K 0.08Mo 11.5Bi 0.4Fe 1.6Ni 6.4Co 1.4La 0.4Rb 0.06W 0.5P 0.04O x?K 0.6Mo 11.5Bi 0.5Fe 1.9Ni 5.2Co 2Ce 0.5Rb 0.07W 0.3V 0.2P 0.025O x?K 0.07Mo 11.8Bi 0.5Fe 2Ni 5.1Co 2La 0.4Cs 0.06V 0.2B 0.2O x?K 0.09Mo 11.3Bi 0.45Fe 1.6Ni 57Co 22La 0.4Rb 0.06W 0.4V 0.3B 0.3P 0.033O x
Annotate: the carrier S iO of above-mentioned catalyzer 2It is 50% (w.t.) table 3.
Selectivity Transformation efficiency Single-pass yield of acrylonitrile
Embodiment 1 embodiment 2 embodiment 3 embodiment 4 embodiment 5 embodiment 6 embodiment 7 embodiment 8 embodiment 9 embodiment 10 ????84.2 ????84.0 ????85.3 ????83.4 ????83.7 ????85.1 ????85.6 ????83.9 ????85.7 ????86.2 ????95.7 ????97.2 ????97.3 ????97.8 ????96.1 ????95.8 ????95.2 ????97.0 ????96.2 ????97.2 ????80.5 ????81.6 ????83.0 ????81.6 ????80.4 ????81.5 ????81.4 ????81.3 ????82.4 ????83.8

Claims (6)

1, a kind ofly is used for the fluid catalyst that propylene, isobutene ammonia oxidizing are produced vinyl cyanide, methacrylonitrile, contain molybdenum, bismuth, iron, nickel, potassium and randomly contain one or more metal oxides in magnesium, brill, calcium, beryllium, lanthanum, cerium, samarium, rubidium, caesium, sodium, boron, tungsten, vanadium and the phosphorus, its active constituent that contains is by following general formula:
K a??Mo b??Bi c??Fe d??Ni e??X f??Y g??Z h??Q i??O x
Wherein:
X is one or more the mixture among Mg, Co, Ca, the Be;
Y is one or more the mixture among La, Ce, the Sm;
Z is one or more the mixture among Rb, Cs, the Na;
Q is one or more the mixture among B, W, P, the V;
A=0～0.5; B=11～13; C, d, e, f, g=0.2～10; H, i=0～2; X satisfies the required Sauerstoffatom sum of other element valence;
The used carrier of catalyzer is silicon-dioxide or aluminum oxide, and its content is (40～60) % (w.t.) of catalyzer total amount.
2, catalyzer according to claim 1 is characterized in that X is Mg or Co or its mixture.
3, catalyzer according to claim 1 is characterized in that Y is La or Ce or its mixture.
4, catalyzer according to claim 1 is characterized in that Z is Rb or Cs or its mixture.
5, catalyzer according to claim 1 is characterized in that Q is W or V or its mixture.
6,, it is characterized in that used carrier is a silicon-dioxide according to claim 1,2,3 or 4 described catalyzer.
CN97106771A 1997-12-11 1997-12-11 Catalyst for propylene and isobutylene ammoxidation fluidized bed Expired - Lifetime CN1055285C (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1101264C (en) * 1999-08-19 2003-02-12 中国石油化工集团公司 Fluidized bed catalyst for preparing acrylonitrile by propene ammonia oxidation
CN100430134C (en) * 2005-08-15 2008-11-05 中国石油化工股份有限公司 Catalyst of fluid bed for preparing ethane and propylene through catalytic cracking
CN100443168C (en) * 2005-08-15 2008-12-17 中国石油化工股份有限公司 Catalyst of fluid bed in use for preparing ethane, propylene through catalytic cracking
CN103657669A (en) * 2012-09-05 2014-03-26 中国石油化工股份有限公司 Fluidized bed catalyst for preparing unsaturation nitrile through ammoxidation and method thereof
CN112121811A (en) * 2019-11-15 2020-12-25 北京水木滨华科技有限公司 Catalyst for preparing methacrylonitrile and method for preparing methacrylonitrile

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101121130B (en) * 2006-08-11 2010-10-27 中国石油化工股份有限公司 Ammoxidation method to manufacturing unsaturated nitrile catalyst

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5457223A (en) * 1992-10-09 1995-10-10 The Standard Oil Company Process for elimination of waste material during manufacture of acrylonitrile

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1101264C (en) * 1999-08-19 2003-02-12 中国石油化工集团公司 Fluidized bed catalyst for preparing acrylonitrile by propene ammonia oxidation
CN100430134C (en) * 2005-08-15 2008-11-05 中国石油化工股份有限公司 Catalyst of fluid bed for preparing ethane and propylene through catalytic cracking
CN100443168C (en) * 2005-08-15 2008-12-17 中国石油化工股份有限公司 Catalyst of fluid bed in use for preparing ethane, propylene through catalytic cracking
CN103657669A (en) * 2012-09-05 2014-03-26 中国石油化工股份有限公司 Fluidized bed catalyst for preparing unsaturation nitrile through ammoxidation and method thereof
CN112121811A (en) * 2019-11-15 2020-12-25 北京水木滨华科技有限公司 Catalyst for preparing methacrylonitrile and method for preparing methacrylonitrile
CN112121811B (en) * 2019-11-15 2021-12-14 北京水木滨华科技有限公司 Catalyst for preparing methacrylonitrile and method for preparing methacrylonitrile

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