CN101284237B - Preparation method of catalyst for acrylonitrile fluid bed - Google Patents

Preparation method of catalyst for acrylonitrile fluid bed Download PDF

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Publication number
CN101284237B
CN101284237B CN2008100507970A CN200810050797A CN101284237B CN 101284237 B CN101284237 B CN 101284237B CN 2008100507970 A CN2008100507970 A CN 2008100507970A CN 200810050797 A CN200810050797 A CN 200810050797A CN 101284237 B CN101284237 B CN 101284237B
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catalyst
span
gram
fluid bed
acrylonitrile
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CN101284237A (en
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于广臣
刘淑杰
林君
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JILIN XINGYUN CHEMICAL CO Ltd OF JILIN CHEMICAL GROUP CORP
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Jihua Group Jilin City Xingyuan Industrial & Trading Co Ltd
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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

Abstract

The invention relates to a catalyst used in acrylonitrile manufacture. The method for preparing the catalyst comprises the processing steps of spray molding, pyrolysis, crystalling phase conversion, and activation roast, and is characterized in that template agent is added in a carrier at first, and the template agent is at least one of tetraethylammonium, tetrapropylammoniumsilicate, polyacrylamide and ethylsilicate; active components are added in the mixing material above mentioned, and the pH value is controlled between 1.5 and 2.5; the mixture is aged before spray molding, the aging temperature ranges from 60 to 120 DEG C, the operating pressure ranges from 0.01 to 0.8Mpa, and the aging time is 1 to 10 hours; the catalyst prepared according to the proposal contains a silicon dioxide carrier and a combination, the chemical formula of which is AaBbCcDdMgeNifBigFehMoiOx calculated on the basis of atomic ratio, wherein, the chemical formula can include Li, K, Cs, Rb, As, B, P, Se, Cu,Sn, Ga, Sr, Ba, Ce, Cr, V, Sb, La and Co. The catalyst has good activity, selectivity, anti-reducibility, and abrasion resistance and can be used in a reactor form a long time, and the service life can even reach more than three years.

Description

Preparation method of catalyst for acrylonitrile fluid bed
Technical field
The present invention relates to a kind of catalyst, more specifically to the acrylonitrile process catalyst.
Background technology
Acrylonitrile is one of important petrochemicals, is mainly used in the manufacturing acrylic fiber, and Sohio method ammoxidation of propylene explained hereafter acrylonitrile is generally adopted in countries in the world, and the key technology in this technology is the fluid catalyst preparation in the reactor.To the research of acrylonitrile fluidized-bed catalyst, the present major part of China concentrates on the composition of chemical analysis, studies high molybdenum active constituent, and fine granularity is in the application of adding on the catalyst, and research α-molybdenum bismuth iron system and γ-molybdenum bismuth iron tie up on the yield of acrylonitrile to be influenced.Find that in the actual production use starting stage activity of some catalyst is higher, use after 6 months that activity obviously reduces, after 18 months, its activity is lower than below 77% substantially, needs to change.
The correlation technique data that the present invention relates to:
Put down in writing in U.S. Pat 6.642.405, US6.653.496, the US6.723.869 file, add citric acid in the preparation mixed salt, its citric acid is surfactant, uses the tension force that can reduce solution in pulping process, promote the formation of molybdenum heteropolyacid, increase porosity simultaneously.
Chinese patent Granted publication number: CN1005248B CN1915500A CN1915499A CN1915501ACN1061166A etc., having told about at molybdenum bismuth iron respectively is to add elements such as sodium, calcium, germanium, chlorine in the active component, form new chemical formula component catalyst, make it to gain in strength, improve activity and selectivity.
Chinese patent: CN1061163A has studied production fine granularity acrylonitrile catalyst, because fine size increases specific area, joins in the body catalyst of use in benefit, improves the activity and the selectivity of acrylonitrile catalyst.
Chinese patent: CN1013079B has studied α-molybdenum bismuth Fe-series catalyst and γ-molybdenum bismuth Fe-series catalyst compares on active and selectivity, confirms that γ-molybdenum bismuth Fe-series catalyst is better than α-molybdenum bismuth Fe-series catalyst.
In above research, acrylonitrile catalyst all adopts traditional handicraft production, and nitrate and carrier silica and molybdenum acid ammonia etc. are made slurry, and is spray-dried, the calcination for activation process, make acrylonitrile fluidized-bed catalyst, not to the carrier existence, how active constituent is distributed between carrier is analyzed, openly the crystalline oxide between active constituent molybdenum and bismuth, iron, the silicon etc. to activity, selectivity, resistance to reduction, achievements in research such as long-time stability.
Prior art is made the method for slurry, is that molybdenum acid ammonia solution is joined in the steady type Ludox of ammonia, adds nitrate solution again and makes slurry.
Total technical process:
Silica adds ammonium molybdate solution, adds the nitrate mixed salt solution again, adjusts pH value then, carries out spray-drying, carries out thermal decomposition, last calcination for activation.
Summary of the invention
The objective of the invention is to overcome the deficiency of prior art, a kind of new preparation method of catalyst for acrylonitrile fluid bed is provided.
Technical scheme of the present invention is: carry out template control moulding on silica supports, pay attention to the adopting process condition simultaneously, impel between active constituent and the carrier atom and have an effect, the crystalline oxides such as silicon molybdenum bismuth iron that formation links to each other with chemical bond, migration path and speed to oxonium ion in the crystal are improved, thereby have improved anti-reducing power.By the control process conditions, increased the adhesion between crystalline oxide and the carrier, improved wear resistence, purpose is to prepare a kind of active steady in a long-term, that the single-pass yield of acrylonitrile rate is higher, selectivity acrylonitrile fluidized-bed catalyst preferably.
Technical process of the present invention:
Silica adds the template agent, adds ammonium molybdate solution and nitrate mixed salt solution again, adjusts pH value, adds thermal aging then, and spray-dried, thermal decomposition, crystalline phase conversion, calcination for activation make this catalyst.
When the present invention has kept former technology, increase the agent of interpolation template, high temperature ageing operation, paid attention to the slurry preparation method of carrier moulding.At first join the template agent in the silica supports by a certain percentage, handle and add ammonium molybdate solution again and after mixing, heat this solution, keep adding under the uniform temperature nitrate solution of different components, adjust pH value after, the intensification ageing, the gained slurry carries out spray drying forming.Obtaining the assorted many salt of grain a bunch shape microspheroidal carrier, active constituent silicon molybdenum bismuth ferrous metal this moment is present between hole and carrier surface with the thin layer state.By thermal decomposition, crystalline phase conversion and calcination for activation, resulting acrylonitrile catalyst, this catalyst carrier is the ball-type particulate of grain bunch shape, active constituent is distributed between the hole of carrier and the surface with crystal state.
A kind of preparation method of catalyst for acrylonitrile fluid bed, comprise spray shaping, thermal decomposition, crystalline phase conversion, calcination for activation processing step, it is characterized in that: at first, the template agent is added in the silica supports, mix and stir, described template agent is at least a in triethylammonium tetrakis, tetrapropyl amine, polyacrylamide, the silester, by weight percentage, consumption is 1%～20% of a silica supports consumption; In above-mentioned batch mixing, add active constituent, mix and stir, control its pH value 1.5～2.5; Before spray shaping, said mixture is carried out ageing, 60～120 ℃ of ageing temperature, operating pressure 0.01～0.8MPa, gauge pressure, digestion time 1～10 hour.
This catalyst contains silica supports and the following composition of atomic ratio measuring chemical formula:
A aB bC cD dMg eNi fBi gFe hMo iO x
A is selected from least a among Li, K, Cs and the Rb in the formula;
B is selected from least a among As, B, P and the Se;
C is selected from least a among Cu, Sn, Ga, Sr and the Ba;
D is selected from least a among Ce, Cr, V, Sb, La, the Co;
The span 0.05～0.5 of a;
The span 0.05～0.5 of b;
The span 0.1～0.5 of c;
The span 0.01～0.25 of d;
The span 0.5～5 of e;
The span 1～10 of f;
The span 0.5～5 of g;
The span 0.5～5 of h;
The value 12.5 of i;
X satisfies the required oxygen atom sum of each element valence in the catalyst;
Described silica, its consumption are 40%～60% of catalyst amount by weight percentage.
The preferred span 0.1～0.3 of a.
The preferred span 0.1～0.3 of b.
The preferred span 0.15～0.3 of c.
The preferred span 0.1～0.2 of d.
The preferred span 1～3 of e.
The preferred span 4～8 of f.
The preferred span 1～3 of g.
The preferred span 1～3 of h.
Before spray shaping, mixture is carried out ageing, 80～100 ℃ of the preferred temperature of ageing, operating pressure 0.2～0.6Mpa, digestion time 4～6 hours.
The silica consumption, preferred span is 45%～55% of catalyst amount by weight percentage.
Acrylonitrile fluidized-bed catalyst by the present invention's preparation has very high active selectivity, resistance to reduction and wear resistence, thereby has guaranteed long-lasting.Can in reactor fluidisation bed, use for a long time, even can reach more than 3 years service life.
The specific embodiment
Below in conjunction with specific embodiment, the present invention is made detailed description further.
Existing processes is, molybdenum acid ammonia solution is joined in the steady type Ludox of ammonia, add nitrate solution again and make slurry, and the present invention is: at first join the template agent in the silica supports by a certain percentage, add ammonium molybdate solution again, heating after mixing, the nitrate solution that adds different components is then adjusted its pH value, 1.5～2.5, carry out ageing again, 60～120 ℃ of ageing temperature, 80～100 ℃ of preferred temperature, ageing pressure is gauge pressure 0.01～0.8MPa, preferred pressure is gauge pressure 0.2～0.6MPa, its time is 1～10 hour, and preferred 4～6 hours time, the present invention is a triethylammonium tetrakis with the template agent, silester, tetrapropyl amine, at least a in the polyacrylamide, its amount is 1%～20% of silica supports consumption by weight percentage.
Provide some comparative examples and specific embodiment below, evaluation on request experimentizes.
Catalyst by embodiments of the invention prepare with the comparative example that provides all adopts unified evaluation method to estimate.
Evaluation method is:
Fluidized-bed reactor Φ 38mm
430 ℃ of reaction temperatures
Reaction pressure 0.084MPa gauge pressure
Catalyst charge weight 420 grams
Catalyst propylene load (WWH) 0.085 hour -1
Raw material proportioning (mole) is a propylene: ammonia: air=1: 1.2: 9.5
Evaluation result all adopts different time sections mean value.
Comparative example 1
Undertaken by example among the CN1005248B 5, its process is summarized as follows (following each example all adopts the summary mode, and the percentage number average before the described solution title belongs to percent concentration), the steady type Ludox of 40% ammonia is adjusted sodium content increase to 100ppm as making raw material.Get 15.3 gram ammonium molybdates and be dissolved in 50 ml waters, 83.2 gram bismuth nitrates are dissolved in 100 milliliters of 1: 1 nitric acid, and both mix to such an extent that a kind of solution is (I).Get 139.8 gram ferric nitrates, 224.6 gram cobalt nitrates, 125.9 gram nickel nitrates, 46.7 milliliter of 50% manganese nitrate, 16.9 milliliter of 10% cesium nitrate and 8.7 gram chromic anhybride mixtures add makes it to be dissolved as (II) in 50 ml waters.351.2 gram ammonium molybdates are dissolved in the raw materials of silica sol that 300 ml waters add the above-mentioned preparation of 1250 grams, add 2.1 gram 45%KOH and (II) add 10.4 gram phosphoric acid again with (I) reaching, abundant stirring pulping, carry out spray drying forming, in 670 ℃ of calcination activations 1 hour, make acrylonitrile fluidized-bed catalyst.
Catalyst is formed:
50％[Cs 0.05K 0.01Ni 2.5Co 0.05Fe 2Mn 1Bi 1Cr 0.05Na 0.4P 0.2Mo 12O x]+50％SiO 2
Evaluation result sees Table 1.
Comparative example 2
Prepare by CN1061163A, adopt CN1005248B] method of comparative example 3 operates, and the consumption of ammonium molybdate increases, there is atomic ratio 12 to be increased to 13.8, strengthen rotating speed in the spray-dried forming process, sintering temperature is increased to 690 ℃ by original 670 ℃, and all the other operating conditions are constant.
Catalyst is formed:
50%[Cs 0.1K 0.1Ni 2Co 0.4Fe 0.9Mn 0.9Cr 0.45Na 0.3Mo 13.8O x]+50%SiO 2Evaluation result sees Table 1.
Comparative example 3
Undertaken by CN1013079B, 15.2 the gram ammonium molybdate is dissolved in 50 ml waters, 83.2 the gram bismuth nitrate is dissolved in 100 milliliters of 1: 1 salpeter solutions, ammonium molybdate solution is joined in the bismuth nitrate solution after stirring, and keep solution temperature to be lower than 55 ℃ making v-bismuth molybdate solution (I).140 gram ferric nitrates, 224.6 gram cobalt nitrates, 126 gram nickel nitrates, 46.7 ml concns, 50% manganese nitrate solution, 16.9 ml concns, 10% cesium nitrate solution mixes and adds 100 ml waters again, heating complete soln (II).Other gets 321.3 gram ammonium molybdates and is dissolved in 250 ml waters, adds the steady type Ludox of 1250 gram 40% ammonia and makes solution (III).2.1 gram 45%KOH and 6.92 gram concentration 40%NaOH solution mixing addings, 817 gram chromium dioxide are made solution (IV).(IV) (II) joined mix in (III) again (I) to be joined then and make slurry in the mixed solution, keep my temperature of slurry to be lower than 55 ℃, carry out spray drying forming by usual method, calcination for activation is 1 hour under 670 ℃ of temperature, makes acrylonitrile fluidized-bed catalyst.
Catalyst is formed:
50％[Bi 2MoO 6]1/2[Cs 0.05K 0.1Ni 2.5Co 0.45Fe 2M 3Na 0.4Mo 11.5O x]+50％SiO 2
Evaluation result sees Table 1.
Comparative example 4
Method by US6.6965.046 is carried out, and gets 196.49 gram ammonium heptamolybdates and is dissolved in 400 ml waters, and the Ludox 625g that will contain concentration 40% silica weight joins in the Ammoniun Heptamolybdate Solution, adds 5.96 gram Sb again 2O 3, add the nitrate mixture at last again, comprise 66.12 gram Fe (NO 3) 29H 2O, 71.3 gram Ni (NO 3) 26H 2O, 83.36 gram Co (NO 3) 26H 2O, 41.96 gram Mg (NO 3) 26H 2O, 19.85 gram Bi (NO 3) 25H 2O, 1.66 gram KNO 3And with 89.7 gram Ce (NH 4) 2(NO 3) 66H 2O is as concentration 50% solution, carries out spray-drying after the slip that reaction generates is concocted, and obtains catalyst thermal decomposition 3 hours in the time of 290 ℃, handles 3 hours in the time of 425 ℃ subsequently, handles obtaining acrylonitrile fluidized-bed catalyst in 3 hours at last in the time of 600 ℃.
The composition of catalyst:
50％[K 0.2Ni 9.0Fe 2.0Bi 0.5Mg 2.0Co 3.5Ce 1.0Sb 0.5Mo 13.6O x]+50％SiO 2
Evaluation result sees Table 1.
Comparative example 5
Undertaken by US6.642.405, get 3000 ml pure waters and add 346.5 gram part ammonium molybdates, then add 4.5 grams, 85% phosphatase 11 .4 gram ABA.Get 38.1 gram bismuth nitrates, 4.0 restrain potassium nitrate, 342.5 gram nickel nitrates, and 62.8 gram chromic nitrates, 34.1 gram cerous nitrates dissolve in 25.0 gram citric acids addings, 270 grams, 3.3% aqueous solution of nitric acid.Get 103 gram ferric nitrates, 25.0 gram citric acids, 270 gram pure water are dissolved to deposit-free.It is 2 that the above material is joined in 2046 gram concentration 20% Ludox with 15% ammoniacal liquor adjustment pH value, fully be heated with stirring to 98 ℃ of constant temperature 1.5 hours, 330 ℃ of spray-drying inlet temperatures, outlet temperature is made catalyst for 160 ℃, 250 ℃ of thermal decompositions 2 hours, 450 ℃ hours, acrylonitrile fluidized-bed catalyst was made in 660 ℃ of roastings in 3 hours.
The composition of catalyst:
50％[Mo 10Bi 0.4Fe 1.3Ni 6Cr 0.8Ce 0.4K 0.2P 0.2B 0.2O x]+SiO 250％
Evaluation result sees Table 1.
Embodiment 1
Get the steady type concentration of 415 gram ammonia 40%SiO 2Ludox adds 17 gram triethylammonium tetrakis and makes the material first through fully stirring; 384.4 the gram ammonium molybdate is dissolved in 200 ml waters, makes material second; 125 gram ferric nitrates, 72.9 gram bismuth nitrates, 331.9 gram nickel nitrates, 100 gram magnesium nitrates, 18.9 gram copper nitrates are dissolved in 600 ml waters, make material third; 1.3 the gram lithium nitrate, 10.9 gram cesium nitrates, 0.7 gram arsenic acid is dissolved in and makes the material fourth in 10 ml waters; To make material second, third, fourth joins in the first, fully stirs, and adjusts pH value to 1.5 with the ammoniacal liquor of concentration 10%, is heated to 80 ℃, he gauge pressure 0.4MPa carries out spray drying forming after 6 hours, change cremator over to, is warming up to 320 ℃, thermal decomposition 2 hours; Be warming up to 420 ℃, crystalline phase conversion 8 hours; Be warming up to 580 ℃, calcination for activation 4 hours is cooled to room temperature behind the calcination for activation, make acrylonitrile fluidized-bed catalyst.
The composition of catalyst:
60％[Li 0.15As 0.05Cu 0.5Ce 0.2Mg 3Ni 9Bi 1.2Fe 2.5Mo 12.5O x]+40％SiO 2
Evaluation result sees Table 1.
Embodiment 2
Get the steady type concentration of 467 gram ammonia 40%SiO 2Ludox adds 24 gram tetrapropyl ammonia and makes the material first through fully stirring; 384.4 the gram ammonium molybdate is dissolved in 200 ml waters, makes material second; 100 gram ferric nitrates, 36.5 gram bismuth nitrates, 258.1 gram nickel nitrates, 66.7 gram magnesium nitrates, 5.6 gram chromic nitrates are dissolved in 600 ml waters, make material third; 1.8 gram potassium nitrate, 0.5 gram boric acid, 4.8 gram beryllium nitrates are dissolved in and make the material fourth in 10 ml waters, will make material second, third, fourth joins in the first, fully stir, ammoniacal liquor with concentration 10% is adjusted pH value to 1.5, is heated to 60 ℃, gauge pressure 0.2MPa, carry out spray drying forming after 8 hours, change cremator over to, be warming up to 290 ℃, thermal decomposition 2 hours; Be warming up to 440 ℃, crystalline phase conversion 6 hours; Be warming up to 600 ℃, calcination for activation 2 hours is cooled to room temperature behind the calcination for activation, make acrylonitrile fluidized-bed catalyst.
The composition of catalyst:
55％[K 0.1B 0.1Ba 0.3Cr 0.25Mg 2Ni 7Bi 0.6Fe 2Mo 12.5O x]+45％SiO 2
Evaluation result sees Table 1.
Embodiment 3
Get the steady type concentration of 518 gram ammonia 40%SiO 2Ludox adds 10 gram polyacrylamides, makes the material first through fully stirring; 384.4 the gram ammonium molybdate is dissolved in 200 ml waters, makes material second; 75 gram ferric nitrates, 109.4 gram bismuth nitrates, 184.4 gram nickel nitrates, 33.3 gram magnesium nitrates, 4.4 gram vanadic acid are dissolved in 600 ml waters, make material third; 1.4 gram phosphoric acid, 2.1 the gram stannic acid, 4.9 gram cesium nitrates are dissolved in and make the material fourth in 10 ml waters, will make material second, third, fourth joins in the first, fully stir, ammoniacal liquor with concentration 10% is adjusted pH value to 2, is heated to 100 ℃, gauge pressure 0.6MPa, carry out spray drying forming after 4 hours, change cremator over to, be warming up to 300 ℃, thermal decomposition 2 hours; Be warming up to 440 ℃, crystalline phase conversion 8 hours; Be warming up to 620 ℃, calcination for activation 2 hours is cooled to room temperature behind the calcination for activation, make acrylonitrile fluidized-bed catalyst.
The composition of catalyst:
50％[Cs 0.2P 0.1Sn 0.1V 0.3Mg 1Ni 5Bi 1.8Fe 1.5Mo 12.5O x]+50％SiO 2
Evaluation result sees Table 1.
Embodiment 4
Get the steady type concentration of 570 gram ammonia 40%SiO 2Ludox adds 34 gram silester, makes the material first through fully stirring; 384.4 the gram ammonium molybdate is dissolved in 200 ml waters, makes material second; 100 gram ferric nitrates, 48.6 gram bismuth nitrates, 221.2 gram nickel nitrates, 50 gram magnesium nitrates, 9.7 gram gallium nitrates are dissolved in 600 ml waters, make material third; 7.1 gram metaantimmonic acid, 5.5 the gram selenic acid, 5.5 gram nitric acid Rubidium are dissolved in and make the material fourth in 10 ml waters, will make material second, third, fourth joins in the first, fully stir, ammoniacal liquor with concentration 10% is adjusted pH value to 2.5, is heated to 100 ℃, gauge pressure 0.6MPa, carry out spray drying forming after 4 hours, change cremator over to, be warming up to 290 ℃, thermal decomposition 2 hours; Be warming up to 450 ℃, crystalline phase conversion 4 hours; Be warming up to 580 ℃, calcination for activation 2 hours is cooled to room temperature behind the calcination for activation, make acrylonitrile fluidized-bed catalyst.
The composition of catalyst:
45％[Rb 0.1Se 0.3Ga 0.3Sb 0.3Mg 1.5Ni 6Bi 0.8Fe 2Mo 12.5O x]+55％SiO 2
Evaluation result sees Table 1.
Embodiment 5
Get the steady type concentration of 623 gram ammonia 40%SiO 2Ludox adds 25 gram silester, makes the material first through fully stirring; 384.4 the gram ammonium molybdate is dissolved in 200 ml waters, makes material second; 150 gram ferric nitrates, 182.3 gram bismuth nitrates, 110.6 gram nickel nitrates, 16.7 gram magnesium nitrates, 5.5 gram cerous nitrates are dissolved in 600 ml waters, make material third; 7.1 gram concentration 85% phosphoric acid, 10.6 the gram stannic acid, 2.4 gram cesium nitrates are dissolved in and make the material fourth in 10 ml waters, will make material second, third, fourth joins in the first, fully stir, ammoniacal liquor with concentration 10% is adjusted pH value to 2, is heated to 60 ℃, gauge pressure 0.2MPa, carry out spray drying forming after 10 hours, change cremator over to, be warming up to 310 ℃, thermal decomposition 2 hours; Be warming up to 460 ℃, crystalline phase conversion 4 hours; Be warming up to 600 ℃, calcination for activation 2 hours is cooled to room temperature behind the calcination for activation, make acrylonitrile fluidized-bed catalyst.
The composition of catalyst:
40％[Cs 0.1P 0.5Sn 0.5Ce 0.1Mg 0.5Ni 3Bi 3Fe 3Mo 12.5O x]+60％SiO 2
Evaluation result sees Table 1.
Embodiment 6
Get the steady type concentration of 467 gram ammonia 40%SiO 2Ludox adds 15 gram tetrapropyl ammonia, makes the material first through fully stirring; 384.4 the gram ammonium molybdate is dissolved in 200 ml waters, makes material second; 75 gram ferric nitrates, 121.5 gram bismuth nitrates, 147.5 gram nickel nitrates, 66.7 gram magnesium nitrates, 10.9 gram lanthanum nitrates are dissolved in 600 ml waters, make material third; 5.3 gram strontium nitrate, 9.2 gram nitric acid Rubidium, 3.7 gram selenic acids are dissolved in and make the material fourth in 10 ml waters, will make material second, third, fourth joins in the first, fully stir, ammoniacal liquor with concentration 10% is adjusted pH value to 2, is heated to 100 ℃, gauge pressure 0.6MPa, carry out spray drying forming after 6 hours, change cremator over to, be warming up to 300 ℃, thermal decomposition 2 hours; Be warming up to 430 ℃, crystalline phase conversion 4 hours; Be warming up to 580 ℃, calcination for activation 2 hours is cooled to room temperature behind the calcination for activation, make acrylonitrile fluidized-bed catalyst.
The composition of catalyst:
55％[Rb 0.5Se 0.2Sr 0.2La 0.2Mg 2Ni 4Bi 2Fe 1.5Mo 12.5O x]+45％SiO 2
Evaluation result sees Table 1.
Embodiment 7
Get the steady type concentration of 570 gram ammonia 40%SiO 2Ludox adds 18 gram polyvinyl lactams, makes the material first through fully stirring; 384.4 the gram ammonium molybdate is dissolved in 200 ml waters, makes material second; 90 gram ferric nitrates, 36.5 gram bismuth nitrates, 221.2 gram nickel nitrates, 83.3 gram magnesium nitrates, 7.4 gram cobalt nitrates are dissolved in 600 ml waters, make material third; 5.6 gram arsenic acid, 0.5 the gram lithium nitrate, 6.5 gram barium nitrates are dissolved in and make the material fourth in 10 ml waters, will make material second, third, fourth joins in the first, fully stir, ammoniacal liquor with concentration 10% is adjusted pH value to 2.5, is heated to 120 ℃, gauge pressure 0.8MPa, carry out spray drying forming after 2 hours, change cremator over to, be warming up to 320 ℃, thermal decomposition 2 hours; Be warming up to 450 ℃, crystalline phase conversion 6 hours; Be warming up to 600 ℃, calcination for activation 2 hours is cooled to room temperature behind the calcination for activation, make acrylonitrile fluidized-bed catalyst.
The composition of catalyst:
45％[Li 0.05As 0.3Ba 0.2Co 0.2Mg 2.5Ni 6Bi 0.6Fe 1.8Mo 12.5O x]+55％SiO 2
Evaluation result sees Table 1.
Embodiment 8
Get the steady type concentration of 518 gram ammonia 40%SiO 2Ludox adds 27 gram triethylammonium tetrakis, makes the material first through fully stirring; 384.4 the gram ammonium molybdate is dissolved in 200 ml waters, makes material second; 125 gram ferric nitrates, 72.9 gram bismuth nitrates, 295 gram nickel nitrates, 100 gram magnesium nitrates, 4.9 gram cerous nitrates, 4.4 gram vanadic acid are dissolved in 600 ml waters, make material third; 3.6 gram potassium nitrate, 2.8 gram concentration 85% phosphoric acid, 6.1 gram cesium nitrates are dissolved in and make the material fourth in 10 ml waters, will make material second, third, fourth joins in the first, fully stir, ammoniacal liquor with concentration 10% is adjusted pH value to 2.5, is heated to 80 ℃, gauge pressure 0.4MPa, carry out spray drying forming after 4 hours, change cremator over to, be warming up to 320 ℃, thermal decomposition 2 hours; Be warming up to 460 ℃, crystalline phase conversion 6 hours; Be warming up to 580 ℃, calcination for activation 2 hours is cooled to room temperature behind the calcination for activation, make acrylonitrile fluidized-bed catalyst.
The composition of catalyst:
50％[K 0.2Cs 0.25P 0.2Ce 0.09V 0.3Mg 3Ni 8Bi 1.2Fe 2.5Mo 12.5O x]+50％SiO 2
Evaluation result sees Table 1.
Figure S2008100507970D00141

Claims (10)

1. a preparation method of catalyst for acrylonitrile fluid bed comprises spray shaping, thermal decomposition, and the crystalline phase conversion, the calcination for activation processing step is characterized in that:
A, at first adds the template agent in the silica supports, mixes and stirs, and described template agent is at least a in polyacrylamide, the silester, and by weight percentage, consumption is 1%～20% of a silica supports consumption;
Add active constituent in B, the above-mentioned batch mixing, mix and stir, control its pH value 1.5～2.5;
C, before spray shaping, above-mentioned mixture is carried out ageing, 60～120 ℃ of ageing temperature, operating pressure 0.01～0.8MPa, gauge pressure, digestion time 1～10 hour.
2. according to the catalyst for acrylonitrile fluid bed of the described preparation method of catalyst for acrylonitrile fluid bed preparation of claim 1, it is characterized in that this catalyst contains silica supports and the following composition of atomic ratio measuring chemical formula:
A aB bC cD dMg eNi fBi gFe hMo iO x
A is selected from least a among Li, K, Cs and the Rb in the formula;
B is selected from least a among As, B, P and the Se;
C is selected from least a among Cu, Sn, Ga, Sr and the Ba;
D is selected from least a among Ce, Cr, V, Sb, La, the Co;
The span 0.05～0.5 of a;
The span 0.05～0.5 of b;
The span 0.1～0.5 of c;
The span 0.01～0.25 of d;
The span 0.5～5 of e;
The span 1～10 of f;
The span 0.5～5 of g;
The span 0.5～5 of h;
The value 12.5 of i;
X satisfies the required oxygen atom sum of each element valence in the catalyst;
Described silica supports, its consumption are 40%～60% of catalyst amount by weight percentage.
3. according to the described catalyst for acrylonitrile fluid bed of claim 2, it is characterized in that the span 0.1～0.3 of a.
4. according to the described catalyst for acrylonitrile fluid bed of claim 2, it is characterized in that the span 0.1～0.3 of b.
5. according to the described catalyst for acrylonitrile fluid bed of claim 2, it is characterized in that the span 0.15～0.3 of c.
6. according to the described catalyst for acrylonitrile fluid bed of claim 2, it is characterized in that the span 0.1～0.2 of d.
7. according to the described catalyst for acrylonitrile fluid bed of claim 2, it is characterized in that the span 1～3 of e.
8. according to the described catalyst for acrylonitrile fluid bed of claim 2, it is characterized in that the span 4～8 of f.
9. according to the described catalyst for acrylonitrile fluid bed of claim 2, it is characterized in that the span 1～3 of g.
10. according to the described catalyst for acrylonitrile fluid bed of claim 2, it is characterized in that the span 1～3 of h.
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