CN104275190A - Catalyst for preparing hydrocyanic acid by adopting methanol ammonia oxidization as well as preparation method and application of catalyst for preparing hydrocyanic acid by adopting methanol ammonia oxidization - Google Patents
Catalyst for preparing hydrocyanic acid by adopting methanol ammonia oxidization as well as preparation method and application of catalyst for preparing hydrocyanic acid by adopting methanol ammonia oxidization Download PDFInfo
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Abstract
The invention discloses a catalyst for preparing hydrocyanic acid by adopting methanol ammonia oxidization as well as a preparation method and application of the catalyst for preparing the hydrocyanic acid by adopting the methanol ammonia oxidization. Most existing catalysts for preparing the hydrocyanic acid by adopting the methanol ammonia oxidization are complicated in structure, inconvenient to prepare and non-ideal in yield. The catalyst disclosed by the invention consists of elements such as molybdenum, bismuth and an oxide of X; the experimental form of the catalyst is MoaBibXcOd, wherein X is one of Fe, K, Ca and Zn; a, b and c are atomic ratios; when a is equal to 1, b is equal to a number from 1 to 2.5, c is equal to a number from 1 to 5, and d is a total number of oxygen atoms in a corresponding oxide generated by chemical combination of catalyst components. The catalyst disclosed by the invention is simple in constituent, high in catalysis activity and stability and convenient to prepare; when the catalyst is applied to preparation of the hydrocyanic acid by adopting the ammonia oxidization, the ammonia oxygen amount is greatly reduced.
Description
Technical field
The present invention relates to industrial chemicals Intermediate Preparation field, specifically a kind of Catalysts and its preparation method and application preparing hydrogen cyanide for methanol ammonoxidation.
Background technology
Hydrogen cyanide is a kind of important industrial chemicals intermediate, can be used for the plating, organic synthesis etc. of preparing nylon, pesticide, acrylonitrile and gold, silver and bronze etc., has the very large market space.
The method of producing hydrogen cyanide mainly contains methane ammonia oxidation, acrylonitrile by-product method, light oil cracking method etc.Methane ammoxidation reaction temperature is more than 1000 DEG C, and hydrogen cyanide productive rate can only reach 60-70%, and reaction temperature is high, brings unsafe factor.Acrylonitrile by-product method is with propylene, air and ammonia for raw material carries out catalytic oxidation synthesis of acrylonitrile, simultaneously by-product part hydrogen cyanide, and due to updating of acrylonitrile catalyst, by-product HCN is fewer and feweri.Light oil cracking method is with light oil, petroleum coke for primary raw material, carries out pyroreaction synthesize hydrogen cyanide with ammonia, and this production technology needs gap to add solid coke, and building-up process is unstable, is difficult to large-scale production.
Therefore, people actively seek other process routes, and methyl alcohol is due to low price, wide material sources, and process route pressure and temp is all in controlled range simultaneously, and methanol ammonoxidation is prepared hydrogen cyanide and is day by day subject to people's attention.In this process route, the factor of most critical is exactly catalyst.
In the existing bibliographical information of hydrogen cyanide, Mo catalyst series has been a kind of catalyst of comparative maturity in methanol ammonoxidation preparation.Mo oxide, no matter as major catalyst or co-catalyst, has the existence of Mo element in most of catalyst.By from different element combinations, Mo catalyst series obtains different performances.As added transition metal to improve activity in active constituent, the list increasing product is received; Add rare earth metal and can improve catalyst activity etc., the improvement of Mo catalyst series is constantly being carried out.
A kind of iron-molybdic catalyst Fe is described in US4425260
amo
bo
c, wherein a=1, b=1-5, c depend on the number of other element oxide oxygen atom, and catalyst baking temperature 750-900 DEG C, the time of baking and banking up with earth is not all 1-3h according to temperature.In optimal conditions, methanol ammonia oxygen is than being 1:1:2.5, and hydrogen cyanide yield is 86.4%.
The catalyst Mo that in US3911089, open catalytic activity is strong
abi
bfe
cx
dy
ez
fo
g, X is the one in Cr, Mn, Co, Ni, Zn, Cd, Sn, W and Pb, and Y is one or several in transition elements.Catalyst preparing temperature 850-900 DEG C, cures time about 6h, for methyl alcohol, formaldehyde or both mixture prepared by ammoxidation for hydrogen cyanide, at air speed 510hr
-1, methanol ammonia oxygen is than being 1:1.1:1.4, and obtaining hydrogen cyanide productive rate is 86%.Ammonia oxygen ratio and the last yield of hydrogen cyanide all undesirable.
A kind of catalyst Mo general in methyl alcohol, propylene, one or more organic matters of isobutene is disclosed in EP0322796
ed
fe
gf
ho
y, D mainly selects from Mn, Fe, Ni, Bi, Zn.Catalyst cures 3h at 850 DEG C, and methanol ammonia oxygen is than under the condition for 1:1.3:4, and HCN yield only has 81%.Mainly study mixed material in the document, when adding 10% formic acid, HCN yield can improve about 5%.But ammonia oxygen methyl alcohol is than too high, and yield is undesirable.
In JP54126698, open methanol ammonoxidation prepares hydrogen cyanide catalyst A
amoBi
bfe
fna
np
po
q, A selects from potassium, rubidium, caesium.The wearability of the main Study of Catalyst of the document, waits reaction condition not illustrate to the ammonia oxygen ratio in course of reaction.In literary composition, catalyst is at 420 DEG C, and under sec1.5s condition, best result selection rate 91.3%, yield is 90.7%.
In addition, the composite catalyst that some more above-mentioned catalyst are slightly complicated is also had.
CN1112243 is to catalyst Mo
abi
bme
cte
dq
er
fx
gy
ho
zstudy, comprise at least one element in the molybdenum of more than 10%, bismuth and chosen from Fe and cerium in catalyst, when tellurium is incorporated in this catalyst, catalyst is at about the 700 DEG C about 3h of roasting, keep the activity of catalyst in the time that can extend, prevent the loss of molybdenum and tellurium simultaneously.Catalyst activity experiment at methanol ammonia oxygen than 1:1:1.2, reaction temperature 420 DEG C, time of contact 0.3s condition under carry out, catalyst stability is good, 50 hours yields 88.5%, yield 88.3% after 500 hours, declines little.But catalyst is more undesirable than overall yield under condition at low ammonia oxygen.
Use catalytic component for Fe in US4461752
acu
bsb
cmo
dme
ete
fq
go
h(SiO
2)
l, reaction condition methanol ammonia oxygen is than 1:1.1:2, and when time of contact is 2-3s, hydrogen cyanide yield can reach 91%, and when contacting during 4s, hydrogen cyanide yield declines obviously, can only reach 76%.
Catalyst Fe in CN1097556
asb
bp
cv
dmo
ecu
fw
gx
hy
iz
jo
k(SiO
2)
1, when methanol ammonia oxygen ratio is for 1:1:1.5, hydrogen cyanide productive rate 94.5%.Do the reaction contact time that this catalyst control experiment increases catalyst, find that the prolongation productive rate along with the reaction time obviously declines.Another this, catalyst structure is complicated, and when preparation composition slightly departs from empirical formula, catalyst performance is degenerated, and hydrogen cyanide productive rate is reduced.
The open catalyst Fe of US5158787
acu
bsb
cv
dmo
ew
fp
gq
hr
is
jo
k(SiO
2)
l, verify in document in the experiment of catalyst, for oxygen than and ammonia be a scope roughly than all, do not carry out detailed research, final cyanic acid yield 80.4-90.1%.
In patent document (comprising above patent document) in recent years, for Mo series catalysts reduce ammonia oxygen in unstripped gas to methanol feedstock than in research little.The reduction of oxygen ratio can improve ultimate yield.The reduction of ammonia ratio produces desirable influence to industrial production everyway, can reduce in and the consumption of sulfuric acid of unreacted ammonia, reduce the production of ammonium sulfate, to reduction production cost and the pollution that controls environment, realize the cleaner production that methanol ammonoxidation prepares hydrogen cyanide, be of great significance.
Therefore, need the Mo catalyst series to methanol ammonoxidation is prepared in hydrogen cyanide process to improve, it is desirable to obtain a kind of Mo series catalysts, at low ammonia oxygen than under condition, have high product yield, also there is good catalytic activity and stability simultaneously.
Further, find out from above-mentioned composite catalyst patent document, composite catalyst combination is complicated, while obtaining several functions, also there is various problems, in the catalyst the influence of every individual element in performance and weight size unknown, the ratio of more difficult grasp catalyst components.Therefore, need to be devoted to the catalyst that development structure has good result simply, simultaneously.
Summary of the invention
Technical problem to be solved by this invention is the defect overcoming the existence of above-mentioned prior art, a kind of new Mo catalyst series preparing hydrogen cyanide for methanol ammonoxidation is provided, this catalyst is when the consumption of ammonia to methyl alcohol is low, hydrogen cyanide also has high yield, and catalyst also has activity and the stability of industrial production needs simultaneously.
For this reason, the present invention adopts following technical scheme: a kind of catalyst preparing hydrogen cyanide for methanol ammonoxidation, is characterized in that, described catalyst is made up of the oxide of molybdenum, bismuth and X, and the empirical formula that this catalyst has is: Mo
abi
bx
co
d,
Wherein, X is the one in Fe, K, Ca, Zn; A, b, c are atomic ratios, and during a=1, b=1 ~ 2.5, c=1 ~ 5, d is the sum of oxygen atom in the corresponding oxide of catalyst component chemical combination generation.
The present invention mainly improves the catalyst taking Mo-Bi as basis.The present inventor carries out finding in the process studied at solution existing issue, mixed the oxide catalyst formed and can be made full use of ammonia by molybdenum, bismuth, iron in the process of methanol ammonoxidation, need the recovery of ammonia hardly, even and if also high yield hydrogen cyanide can be obtained under the condition of low ammonia/methyl alcohol.
The present invention was used as research to component each in catalyst, and find that Bi is the key component of catalytic activity, not containing the catalyst of Bi, hydrogen cyanide yield is very low; And find that Bi proportion of composing in the catalyst has important impact for the activity of catalyst and stability.By the mass ratio that adjustment Bi element occupies in the catalyst, obtain at low ammonia oxygen than condition stability inferior and active all more outstanding catalyst.
Find, containing in the catalyst of Mo, Bi, the element such as Bi and K, Fe, Ca, Zn coexists, and can produce favourable synergy, does not need to add other unnecessary promoter elements simultaneously, just can obtain the effect that we need.
Further, the atomic ratio of described X and Bi is preferably 0.5-3:1, most preferably is 1-2:1.Research finds that the ratio of Bi and X element is very important, excessive the adding of X element, and namely X/Bi ratio is larger, only product yield can be caused to reduce, reduce the utilization to ammonia simultaneously.Therefore, the optimization of the proportionate relationship between the present invention needs by Bi and X element, obtains the catalyst that effect is best.
The mechanism of action for catalyst can from electro transfer angle analysis.In methanol ammonoxidation catalytic oxidation, composition Mo is catalyst body, in methyl alcohol, introduce ammonia, carries whole catalyst and the formation of methanol intermediate complex; Composition Bi, as co-catalyst, plays the effect improving catalyst choice and stability, thus makes the activity that catalyst keeps considerable; Component X (Fe, K, Ca, Zn), as electron deficient element, plays a part in the catalyst to shift oxygen atom, transfers in catalyst by free oxygen molecule, becomes the Lattice Oxygen that can participate in reacting.
Secondly, the invention provides the preparation method of above-mentioned catalyst, its step is as follows: be dissolved in the water by the raw material as catalyst component, adds chelating agent and fully mixes, and heat treatment forms slurry, by slurry spraying dry, obtains catalyst granules; By catalyst granules at 250-400 DEG C of temperature after preliminary calcining 1-10h, at the temperature calcination 1 ~ 12 hour of 500 ~ 800 DEG C;
As the raw material of catalyst molybdenum composition, select in molybdenum oxide, molybdenum chloride, nitric acid molybdenum, carbonic acid molybdenum, oxalic acid molybdenum, molybdenum phosphate one or more, be preferably molybdenum chloride;
As the raw material of catalyst bismuth composition, select in bismuth oxide, waltherite, bismuth nitrate, bismuth oxalate one or more, be preferably waltherite;
As the raw material of catalyst X composition, select its oxide, inorganic acid salt or acylate, preferred nitrose inorganic acid salt.
Catalyst composition of the present invention is simple, easy to prepare, and catalyst routine techniques can be used to prepare.Slurry spraying dry, can select conventional spray-drying installation such as pressurization nozzle type, rotating disk formula etc.In spray-dired process, need suitably to regulate slurry concentration and spray drying condition, according to production object, the particle of obtained required domain size distribution.Finally by the temperature calcination 1 ~ 12 hour of catalyst at 500 ~ 800 DEG C, excellent activity can be reached.Calcining heat is lower than 500 DEG C, and catalytic activity is not enough; Higher than 800 DEG C, increase as particle tack during fluidized-bed catalyst, catalyst calcination is uneven.
The present invention wishes that the preparation method by changing catalyst obtains the good performance of catalyst, found by research and great many of experiments, by adding chelating agent, chelating agent and catalyst is made to produce complex coordination effect, the physical property of catalyst constituent can be changed, thus make catalyst possess more excellent redox ability, reduce the burning of ammonia, thus reduce ammonia ratio.
The initiation material forming catalyst components is the material that just will can become each component oxide in catalyst after chemical treatment, calcination processing.Specifically can select from the various materials such as their oxide, hydroxide, chloride, nitrate and acylate.
Further, as the raw material of catalyst X composition, select in di-iron trioxide, tri-iron tetroxide, calcium oxide, zinc oxide, frerrous chloride, zinc chloride, calcium carbonate, ferric nitrate, oxalates, citrate one or more.
Further, described chelating agent is the one in sodium thiosulfate, triethanolamine, ethylenediamine, citric acid, lactic acid, tartaric acid, grape acid, and the addition of chelating agent accounts for the 8-15% of material quality, is preferably 10%.
Further, after chelating agent fully mixes and between heat treatment formed before slurry, add carrier solution and fully stir, this carrier is the one in titanium oxide, zirconia or silica, preferred silica.
Catalyst of the present invention can without carrier, also available support.Use 10 ~ 90% (wt) that carrier amount is catalyst total amount.
Again, the invention provides the application of above-mentioned catalyst, under catalyst action, methyl alcohol carries out gas phase with molecular oxygen and ammonia and contacts in catalyst oxidation reactor, prepared by ammoxidation is for hydrogen cyanide, and reaction temperature is 400-450 DEG C, and reaction pressure is normal pressure, the mol ratio of molecular oxygen/methyl alcohol is 1.0-1.5:1, and the ratio of ammonia/methyl alcohol is 0.9-1.1:1; Described methyl alcohol is steam state.
Further, described catalyst oxidation reactor is calandria type fixed bed catalyst oxidation reactor or shell and tube fluidized bed catalyst oxidation reactor, preferred calandria type fixed bed catalyst oxidation reactor; Described molecular oxygen is the one in air, oxygen rich gas, purity oxygen, economically preferred air.Gas and vapor permeation adopts Venturi tube mixer.
Catalyst of the present invention forms simple and has good catalytic activity and stability, and when the consumption of ammonia to methyl alcohol is low, hydrogen cyanide also has high yield; Catalyst easy to prepare, can use catalyst routine techniques to prepare; Apply catalyst ammonia of the present invention oxidation and prepare hydrogen cyanide, ammonia oxygen amount used obtains and significantly reduces, thus decrease the consumption of acid neutralizing the ammonia that has neither part nor lot in reaction and use, to reduction production cost and the pollution that controls environment, realize the cleaner production that methanol ammonoxidation prepares hydrogen cyanide, be of great significance.
Detailed description of the invention
Following use non-limiting example further will be set forth the present invention.
Embodiment 1 (catalyst 1)
23.5g molybdenum chloride is dissolved in 300ml water and forms solution, add 85.0g bismuth nitrate and 54.5g ferric nitrate wherein in batches, form mixed solution with 16.3g ethylenediamine (gross mass 10%).
Under well-beaten condition, add in mixed solution by 82g Ludox (gross mass 50%), while stirring, under 100 DEG C of conditions, heat treatment forms slurry.Use disc type spray dryer that slurry is carried out spraying dry afterwards.Meticulous for gained spherical particle is calcined 6h at 200 DEG C, at 750 DEG C, calcines 1h.
The catalyst of preparation obtains following empirical formula:
Mo
1Bi
1.5Fe
2.6O
36.9(SiO
2)
1.35
Embodiment 2 (catalyst 2)
24.4g molybdenum oxide is dissolved in 300ml water and forms solution, add 98.5g bismuth nitrate and 91.5g iron chloride wherein in batches, form mixed solution with 17.15g grape acid (8%).
Under well-beaten condition, add in mixed solution by 192.96 Ludox (90%), while stirring, under 100 DEG C of conditions, heat treatment forms slurry.Use disc type spray dryer that slurry is carried out spraying dry afterwards.Meticulous for gained spherical particle is calcined 4h at 250 DEG C, at 700 DEG C, calcines 2h.
The catalyst of preparation obtains following empirical formula:
Mo
1Bi
1.2Fe
2O
31.8(SiO
2)
3.21
Embodiment 3 (catalyst 3)
32.5g nitric acid molybdenum is dissolved in 300ml water and forms solution, add 79.75g waltherite and 56.0g calcium carbonate wherein in batches, form mixed solution with 37.2g lactic acid (15%).
Under well-beaten condition, add in mixed solution by 148.8g Ludox (60%), while stirring, under 100 DEG C of conditions, heat treatment forms slurry.Use disc type spray dryer that slurry is carried out spraying dry afterwards.Meticulous for gained spherical particle is calcined 3h at 300 DEG C, at 650 DEG C, calcines 3h.The catalyst of preparation obtains following empirical formula:
Mo
1Bi
1.5Ca
2.68O
18.54(TiO
2)
1.26。
Embodiment 4 (catalyst 4)
65.8g nitric acid molybdenum is dissolved in 300ml water and forms solution, add 83.1g waltherite and 34.5g calcium oxide wherein in batches, form mixed solution with 22g citric acid (12%).
Under well-beaten condition, add in mixed solution by 73.36g titanium oxide (40%), while stirring, under 100 DEG C of conditions, heat treatment forms slurry.Use disc type spray dryer that slurry is carried out spraying dry afterwards.Meticulous for gained spherical particle is calcined 2h at 350 DEG C, at 600 DEG C, calcines 4h.The catalyst of preparation obtains following empirical formula:
Mo
1Bi
1.75Ca
3.3O
15.05(TiO
2)
0.92。
Embodiment 5 (catalyst 5)
62.5g molybdenum chloride is dissolved in 300ml water and forms solution, add 96.5g bismuth oxide and 50.8g potash wherein in batches, form mixed solution with 20.98g tartaric acid (10%).
Under well-beaten condition, add in mixed solution by 20.98g zirconia (10%), while stirring, under 100 DEG C of conditions, heat treatment forms slurry.Use disc type spray dryer that slurry is carried out spraying dry afterwards.Meticulous for gained spherical particle is calcined 1h at 400 DEG C, at 550 DEG C, calcines 5h.The catalyst of preparation obtains following empirical formula:
Mo
1Bi
1.34K
2.38O
5.58(ZrO
2)
0.17
Embodiment 6 (catalyst 6)
35.6g molybdenum oxide is dissolved in 300ml water and forms solution, add 208g bismuth oxide and 64.6g potassium chloride wherein in batches, form mixed solution with 24.5g sodium thiosulfate (12%).
Under well-beaten condition, add in mixed solution by 204.2g zirconia (80%), while stirring, under 100 DEG C of conditions, heat treatment forms slurry.Use disc type spray dryer that slurry is carried out spraying dry afterwards.Meticulous for gained spherical particle is calcined 4h at 250 DEG C, at 500 DEG C, calcines 4h.The catalyst of preparation obtains following empirical formula:
Mo
1Bi
1.8k
3.5O
2.7(ZrO
2)
2
Embodiment 7 (catalyst 7)
86.8g carbonic acid molybdenum is dissolved in 300ml water and forms solution, add 202.5g bismuth oxalate and 85.7g zinc oxide wherein in batches, form mixed solution with 30g triethanolamine (8%).
Under well-beaten condition, do not add carrier solution, while stirring, under 100 DEG C of conditions, heat treatment forms slurry.Use disc type spray dryer that slurry is carried out spraying dry afterwards.Meticulous for gained spherical particle is calcined 3h at 300 DEG C, at 800 DEG C, calcines 1h.
The catalyst of preparation obtains following empirical formula:
Mo
1Bi
1.07Zn
1.89O
11.31
Embodiment 8 (catalyst 8)
78.6g nitric acid molybdenum is dissolved in 300ml water and forms solution, add 179.25g bismuth oxalate and 115.5g zinc chloride wherein in batches, form mixed solution with 33.6g tartaric acid (9%).
Under well-beaten condition, do not add carrier solution, while stirring, under 100 DEG C of conditions, heat treatment forms slurry.Use disc type spray dryer that slurry is carried out spraying dry afterwards.Meticulous for gained spherical particle is calcined 3h at 300 DEG C, at 700 DEG C, calcines 2h.The catalyst of preparation obtains following empirical formula:
Mo
1Bi
2.3Zn
3.8O
15.05
Comparative example 1-4 (comparative catalyst 1-3)
Adopt with the same method for preparing catalyst of embodiment 1-4, in the constituent of catalyst, the ratio of X element and bismuth increases, and obtains following empirical formula:
Comparative example 1:Mo
1bi
1.5fe
1.23o
24.57(SiO
2)
1.12
Comparative example 2:Mo
1bi
1.2fe
2.95o
31.8(SiO
2)
3.86
Comparative example 3:Mo
1bi
1.5ca
4.5o
24(TiO
2)
1.55
Comparative example 4:Mo
1bi
1.75ca
4.4o
16.15(TiO
2)
0.97
Comparative example 5-8 (comparative catalyst 5-8)
Adopt with the same catalyst composition of embodiment 5-8 and preparation condition, just do not add chelating agent during mixing of materials.
The performance test of catalyst
Liquefied ammonia decompression enters static mixer for gaseous state and excess air are mixed, and liquid methanol passes into.Be heated to the calandria type fixed bed catalyst oxidation reactor that 300 DEG C of feedings fill in catalyst, react at 400 ~ 450 DEG C.Reaction pressure is normal pressure, time of contact 0.1-0.5s, oxygen methyl alcohol is than 1.0 ~ 1.5:1, and ammonia methyl alcohol is than 0.9 ~ 1.1:1.Catalytic reaction discharging is through deamination, and after absorption, rectifying obtains finished product.
Catalyst composition prepared by embodiment 1-6 and comparative example 1-6 (being called for short comparative example 1-6) and performance test conditions are listed in the table below 1, Catalyst Activating Test is as follows: loading catalyst in a tubulation of fixation reaction bed, height 1.5m, sends into mixed raw material gas.
The performance test of catalyst needs to use following three concepts:
The conversion ratio of methyl alcohol, the yield of hydrogen cyanide and selection rate have following definitions.
The yield (100%) of hydrogen cyanide
=(the carbon weight of the hydrogen cyanide of formation)/(the carbon weight of the methyl alcohol added) × 100.
The conversion ratio (100%) of methyl alcohol
=(the carbon weight of the methyl alcohol reacted)/(the carbon weight of the methyl alcohol added) × 100.
Selective (100%) of hydrogen cyanide
=(hydrogen cyanide yield)/(methanol conversion) × 100.
Table 1
Afterwards at the conditions of the experiments described above, carry out the test of methanol ammonoxidation reaction stability with catalyst in above-mentioned catalyst 4 (embodiment 4), comparative example 4 and comparative example 8, the results are shown in Table 2:
Table 2
Claims (10)
1. prepare a catalyst for hydrogen cyanide for methanol ammonoxidation, it is characterized in that, described catalyst is made up of the oxide of molybdenum, bismuth and X, and the empirical formula that this catalyst has is: Mo
abi
bx
co
d,
Wherein, X is the one in Fe, K, Ca, Zn; A, b, c are atomic ratios, and during a=1, b=1 ~ 2.5, c=1 ~ 5, d is the sum of oxygen atom in the corresponding oxide of catalyst component chemical combination generation.
2. catalyst according to claim 1, is characterized in that, the atomic ratio of described X and Bi is 0.5-3:1.
3. catalyst according to claim 2, is characterized in that, the atomic ratio of described X and Bi is 1-2:1.
4. the preparation method of catalyst described in any one of claim 1-3, it is characterized in that, it comprises the following steps:
Be dissolved in the water by raw material as catalyst component, add chelating agent and fully mix, heat treatment forms slurry, by slurry spraying dry, obtains catalyst granules; By catalyst granules at 250-400 DEG C of temperature after preliminary calcining 1-10h, at the temperature calcination 1 ~ 12 hour of 500 ~ 800 DEG C;
As the raw material of catalyst molybdenum composition, select in molybdenum oxide, molybdenum chloride, nitric acid molybdenum, carbonic acid molybdenum, oxalic acid molybdenum, molybdenum phosphate one or more;
As the raw material of catalyst bismuth composition, select in bismuth oxide, waltherite, bismuth nitrate, bismuth oxalate one or more;
As the raw material of catalyst X composition, select its oxide, inorganic acid salt or acylate.
5. preparation method according to claim 4, it is characterized in that, as the raw material of catalyst X composition, select in di-iron trioxide, tri-iron tetroxide, calcium oxide, zinc oxide, frerrous chloride, zinc chloride, calcium carbonate, ferric nitrate, oxalates, citrate one or more.
6. preparation method according to claim 4, is characterized in that, described chelating agent is the one in sodium thiosulfate, triethanolamine, ethylenediamine, citric acid, lactic acid, tartaric acid, grape acid, and the addition of chelating agent accounts for the 8-15% of material quality.
7. preparation method according to claim 6, is characterized in that, the addition of described chelating agent accounts for 10% of material quality.
8. preparation method according to claim 4, is characterized in that, after chelating agent fully mixes and between heat treatment formed before slurry, add carrier solution and fully stir, this carrier is the one in titanium oxide, zirconia or silica.
9. the application of catalyst described in any one of claim 1-3, it is characterized in that, under catalyst action, methyl alcohol carries out gas phase with molecular oxygen and ammonia and contacts in catalyst oxidation reactor, prepared by ammoxidation is for hydrogen cyanide, and reaction temperature is 400-450 DEG C, and reaction pressure is normal pressure, the mol ratio of molecular oxygen/methyl alcohol is 1.0-1.5:1, and the ratio of ammonia/methyl alcohol is 0.9-1.1:1; Described methyl alcohol is steam state.
10. application according to claim 9, is characterized in that, described catalyst oxidation reactor is calandria type fixed bed catalyst oxidation reactor or shell and tube fluidized bed catalyst oxidation reactor; Described molecular oxygen is the one in air, oxygen rich gas, purity oxygen.
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| CN106669705A (en) * | 2016-12-26 | 2017-05-17 | 阳泉煤业（集团）有限责任公司 | Catalyst used for methanol ammoxidation and preparation and forming method thereof |
| WO2018141826A1 (en) * | 2017-02-06 | 2018-08-09 | Haldor Topsøe A/S | Production of acetonitrile and/or hydrogen cyanide from ammonia and methanol |
| CN110272021A (en) * | 2018-03-13 | 2019-09-24 | 国家能源投资集团有限责任公司 | Catalyst for methanol protective agent and preparation method thereof |
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| CN114100652A (en) * | 2021-12-10 | 2022-03-01 | 北京道思克矿山装备技术有限公司 | Catalyst for producing hydrogen cyanide by methanol gas phase catalytic ammoxidation, and preparation method and application thereof |
| CN114917918A (en) * | 2022-06-21 | 2022-08-19 | 临沭县华盛化工有限公司 | Special iron-molybdenum catalyst in hydrocyanic acid production process and preparation method |
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| CN106669705A (en) * | 2016-12-26 | 2017-05-17 | 阳泉煤业（集团）有限责任公司 | Catalyst used for methanol ammoxidation and preparation and forming method thereof |
| WO2018141826A1 (en) * | 2017-02-06 | 2018-08-09 | Haldor Topsøe A/S | Production of acetonitrile and/or hydrogen cyanide from ammonia and methanol |
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| CN110272021A (en) * | 2018-03-13 | 2019-09-24 | 国家能源投资集团有限责任公司 | Catalyst for methanol protective agent and preparation method thereof |
| CN112808160A (en) * | 2020-12-23 | 2021-05-18 | 陕西科技大学 | Preparation method of double-oxide nano-agglomeration spraying composite powder |
| CN112808160B (en) * | 2020-12-23 | 2022-07-19 | 陕西科技大学 | Preparation method of double-oxide nano-agglomeration spraying composite powder |
| CN114029094A (en) * | 2021-11-03 | 2022-02-11 | 华阳新材料科技集团有限公司 | Catalyst forming method |
| CN114100652A (en) * | 2021-12-10 | 2022-03-01 | 北京道思克矿山装备技术有限公司 | Catalyst for producing hydrogen cyanide by methanol gas phase catalytic ammoxidation, and preparation method and application thereof |
| CN114100652B (en) * | 2021-12-10 | 2023-10-13 | 北京道思克矿山装备技术有限公司 | Catalyst for producing hydrogen cyanide by methanol gas-phase catalytic ammoxidation and preparation method and application thereof |
| CN114917918A (en) * | 2022-06-21 | 2022-08-19 | 临沭县华盛化工有限公司 | Special iron-molybdenum catalyst in hydrocyanic acid production process and preparation method |
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Inventor after: Chen Cong Inventor after: Chen Zhirong Inventor after: Wang Yong Inventor after: Wang Zhengjiang Inventor after: Wang Zhixuan Inventor after: Sheng Yidong Inventor after: Zhang Lifu Inventor before: Chen Cong Inventor before: Chen Zhirong Inventor before: Wang Zhixuan Inventor before: Sheng Yidong Inventor before: Zhang Lifu |