CN1579631A - External activating method of cis-butenedioic anhydride catalyst - Google Patents
External activating method of cis-butenedioic anhydride catalyst Download PDFInfo
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Abstract
The invention provides activator activation technology out of implement, provides several kinds of vanadium and molybdenum activator technic method of oxidation of benzene to produce arranged anhydride. Its activation method is setting the activator in a subminiature solid phase reactor, then put the reactor into the activator even, and complete the process after high temperature calcinations. Compared to the benzene activator process in the benzene oxidation reactor, the process can be called new activator technic out of vessel. The main technic condition is activator temperature, 400-500 deg.C; activator time, 2-10h; the activator atmosphere is the air with ammonia, the proportion of ammonia and air is 1:25-1:5. The method of this invention, can save a lot of energy of consumer, reduce equipment, decrease the technical demand of the reactor; at the same time, it can increase the coat fastness of the activator, increase the conversion of benzene and arranged anhydride acceptance rate; it can mitigate the poison to operators greatly, because of no vanadium powder.
Description
Technical field
The present invention relates to catalyst technical field, particularly a kind of activating process method of various vanadium-molybdenum catalysts of fixed bed benzene preparing cis-butenedioic anhydride by oxidation.
Background technology
The fixed bed benzene oxidation maleic anhydride catalyst of production and sales both at home and abroad all must have activation process before use at present.This activation process has plenty of by catalyst user (being the cis-butenedioic anhydride producer) and finishes in reactor, and this is activation in the device; And the activation process of having been finished by Catalyst Production person before catalyst dispatches from the factory belongs to outside the device and activates.
Propose to handle at 500 ℃ in the early stage day disclosure special permission 2353136 with gases such as hydrogen, carbon monoxide, methane, hydrogen sulfide.This requires the cis-butenedioic anhydride producer except that preparing raw material, and the device that produces hydrogen, carbon monoxide also must be set.Because the gaseous species difference can be influential to reactor material, thereby must activate in other stove.And the activation gas of separating out directly enters atmosphere and is harmful to, and also need set up corresponding processing means as head it off.
The method of introducing in the Japanese kokai publication sho 53-1190 communique is to activate in reactor, use the hydrocarbon except that normal butane without the cis-butenedioic anhydride raw material, this also will prepare special device, and produces inactive gas, and the waste gas of generation enters in the atmosphere also harmful after the activation.
Day disclosure special permission communique, the spy opens and proposes among the flat 4-326942 to activate in the reactor of cis-butenedioic anhydride factory, and requiring temperature of molten salt is 410,420 or 430 ℃, air speed 1000h
-1, atmosphere is the air that contains benzene, benzene concentration is 17g/M
3, soak time is 24-36h.This is just higher to the material and the process technology requirement of reactor, the temperature of molten salt (fused salt seeping at high temperature extremely strong) of ability more than 430 ℃.Also the furnace system that goes into operation need be set, it is about 3% to increase construction investment, and programming rate is often very slow in whole temperature-rise period, generally needs 2-5 days, insulation 24-48h.Expend a large amount of energy (electricity, fuel) like this, the time that has delayed product simultaneously.
The mid-80 has one piece of European patent 86104086.3 about the cis-butenedioic anhydride production technology to mention maleic anhydride catalyst after the spraying active component, can be at 400-450 ℃, and calcination 4-8h in air or air stream.This activation should belong to device and activate outward, but atmosphere is oxidizing atmosphere, and this will cause the valence state of vanadium to raise, and then can reduce the benzene conversion ratio and the yield of maleic anhydride of catalyst, therefore the serviceability temperature of catalyst is than higher, and the catalyst activity that this activation method is produced is lower.Here do not have outer equipment, the technology that activates of resolver, especially do not recognize the necessity of reducing atmosphere.
The domestic main at present producer that produces maleic anhydride catalyst is Zhong He chemical plant and Beijing Chemical Research Institute, still adopt activation method in the device, make cis-butenedioic anhydride manufacturer activate upslide at catalyst and go into a lot of human and material resources and financial resources, activity of such catalysts can not get good utilization simultaneously.
Summary of the invention
The invention provides the outer activating technology of catalyst device, solved a difficult problem that is always perplexing maleic anhydride catalyst manufacturer and cis-butenedioic anhydride manufacturer.The activating process method of the various vanadium-molybdenum catalysts of benzene preparing cis-butenedioic anhydride by oxidation is provided.
The present invention is achieved in that
Benzene gas phase catalytic oxidation is made the catalyst of cis-butenedioic anhydride and is finished the activating process process at catalyst manufacturer.Its activation method is that catalyst is placed a kind of miniature solid phase reactor, again this reactor is put into the activation furnace high temperature sintering and is finished activation process.With respect to the band benzene activation process of user in the benzene oxidation reactor, this activation process can be described as the outer activating process of novel device.The main technique condition is: activation temperature, 400-500 ℃; Soak time, 2-10h; Activation phenomenon is the air that contains ammonia, and ammonia is empty than being 1: 25-1: 5.。
Above-mentioned catalyst is meant with benzene to be raw material is made the different shape carrier of cis-butenedioic anhydride through the gas phase tubular fixed-bed reactor vanadium-molybdenum catalyst.This catalyst belongs to carried catalyst, and carrier is artificial synthetic green silicon carbide or alundum (Al; Active component is by vanadic anhydride (V
2O
5), molybdenum trioxide (MoO
3), phosphorus pentoxide (P
2O
5), sodium oxide molybdena (Na
2O), nickel oxide (NiO) and a kind of, two kinds or three kinds of rare earth oxide (Re
2O
3) form.Mol ratio between each component is: V
2O
5: MoO
3: P
2O
5: Na
2O: NiO: Re
2O
3=1: 0.4-0.9: 0.005-0.09: 0.01-0.09: 0.005-0.5: 0.0001-0.002.
The above-mentioned ammonia air that contains is meant in miniature solid phase reactor, can not in time flow out the outer reducing atmosphere that contains finite concentration ammonia that forms of device thereby catalyst self decomposes the ammonia that produces owing to high temperature action in device.Generally ammonia is empty than being 1 between temperature raising period: 25-1: 15, and be 1 between soak: 10-1: 5.
Activation temperature of the present invention is between 400-500 ℃, and preferred range is 410-460 ℃.Soak time is between 2-10h, and preferred soak time is 2-7h.
Above-mentioned activation temperature 400-500 ℃, preferably the programming rate with 2-3 ℃/min progressively reaches, and after the insulation 2-6h, the cooling rate with 10 ℃/min drops to normal temperature again.
Operation principle of the present invention is: the oxide that is produced in the decomposable process is because the gas of self emitting (for example, the ammonia of emitting during the heat treatment ammonium salt) and be reduced.Reduction degree depends on heat treated condition, in no oxygen medium, increases with the temperature rising; And in oxygen medium is arranged, a maximum then will appear, this value with make this compound reduction with the ammonia of overflowing and make the as-reduced compound of part reoxidize the ratio of the two relative speed with oxygen in the air relevant.Because the activity and the selectivity of reduction degree and vanadium-molybdenum catalyst have direct relation, so be crucial for adopting what activation phenomenon in the maleic anhydride catalyst activation process.
Activating process method of the present invention is applicable to the activation process of all types of vanadium-molybdenum catalysts of benzene gas phase fixed bed catalytic oxidation manufacturing cis-butenedioic anhydride.Here the indication maleic anhydride catalyst is meant the carried catalyst that contains vanadium, molybdenum, phosphorus, sodium, nickel and other element oxide usually, and carrier material and shape are without limits.
Catalyst behind the load active component is packed in the solid phase reactor.This solid phase reactor should be accomplished can not circulate smoothly with the device outer air, but is not airtight.The catalyst ammonia that produces that is decomposed in this reactor can not be overflowed rapidly, and form the certain density ammonia air that contains therein, thereby formation reducing atmosphere, solid phase reactor is outward that the calcination furnace air can not circulate outward with stove unblockedly simultaneously, makes by adjustable sealing device to form in the incinerator and the outer stale air atmosphere (being oxidizing atmosphere) of stove.
With individual the sending into respectively in the activation furnace of solid phase reactor 2-20 of having adorned catalyst and loam cake being built, after fire door shut, regulating sealing device can not smooth and easyly circulate the stove inner air and outer air, the sealing device of fire door can adopt different encapsulants, as asbestos, temperature resistant rubber etc., activation phenomenon is meant the gas phase composition in the solid phase reactor, require to form the air that contains ammonia, this seal degree by the control solid phase reactor reaches, empty than being 1 by ammonia between chromatography control soak: 10-1: 5, slowly intensification then.
Activation method of the present invention will be controlled the weightless ratio of catalyst, generally is controlled at 0.2-2.0%, is preferably 0.6-1.5%.
The present invention can adopt following equipment:
As shown in Figure 1, an incinerator 1 that is provided with three layers of support 4 is provided with in the incinerator and is provided with electric heater unit 5 in heat-insulation layer 6, the heat-insulation layer, fire door 2 is provided with temperature resistant rubber sealing strip 3; Every layer of support is provided with solid phase reactor 8, and each reactor is provided with digital temp controlled meter 7 control temperature.
Be provided with dividing plate 11 in each reactor 8, reactor is divided into 9 zones, reactor bottom and be provided with the micropore 12 of 0.5mm diameter all around, the reactor upper edge is provided with sealing ring 10, as shown in Figure 2.
Loam cake is provided with the connecting bolt 14 that is connected with the sealing ring of reactor upper edge, as shown in Figure 3.
The outer activation method of device of the present invention can make maleic anhydride catalyst user (being cis-butenedioic anhydride factory) save a large amount of energy, and minimizing equipment reduces the specification requirement to reactor; Simultaneously, the coat fastness of catalyst be can increase, benzene conversion ratio and yield of maleic anhydride improved; Owing to do not have the dust of vanadium, can alleviate the murder by poisoning of loading catalyst greatly to operating personnel.
Description of drawings
Fig. 1: catalyst activator half sectional view;
Fig. 2: solid phase reactor body schematic diagram;
Fig. 3: solid phase reactor vertical view.
The specific embodiment
Embodiment 1:
A, preparing carriers
Take by weighing 800g respectively and cross the green silicon carbide powder of 70 mesh sieves, 200g crosses the low pressure china clay of 100 mesh sieves, and the 66.4g molecular weight is the methylcellulose of 20-40, and 133.6g crosses the polypropylene powder of 40-80 mesh sieve, evenly mixes in the barrel of packing into successively.In addition, take by weighing 200mL90-4 number and contain SiO
224% Ludox is dissolved in the 200ml distilled water.Then, fully mediate, place 24h both mixings of putting together.On the carrier make-up machine, make the annular carrier of cylinder then.After the carrier oven dry with moulding, place a high-temperature electric resistance furnace,, after the cooling, obtain finished product carborundum cylinder ring carrier naturally at 1325 ± 15 ℃ of calcination 8h.Carrier dimensions is: external diameter 6.5mm, internal diameter 3.5mm, height 4.0mm.The Main physical performance indications of carrier: bulk density 0.67 ± 0.02g/ml, the horizontal 2-5kg/ grain of some pressure, vertical 8-20kg/ grain, specific surface 0.08-0.2m
2/ g, Na in the carrier
2The content of O≤0.3%.
B, the preparation of active matter solution
93.23g oxalic acid is dissolved in the 380ml water at normal temperature and under stirring, adds the 74.6g ammonium metavanadate again, heating is all dissolved up to solids while stirring; And then the ammonium paramolybdate that adds 33.70g is dissolved in the solution of 62ml water; Under agitation add tertiary sodium phosphate 4.86g more successively, nickel nitrate 1.403g and neodymium oxide 0.0542g obtain blackish green transparent active matter solution at last.
C, Preparation of Catalyst
At first 280g is put into a rotatable heatable stainless steel rotary drum by the carrier of above-mentioned A method manufacturing.Constantly rotating under the continuous heating condition, will spray on the surface of carrier in the rotary drum by a special spray gun by the active matter solution of above-mentioned B method preparation.270 ± 15 ℃ of spraying temperatures, spray time 90min.Cooling takes the dish out of the pot slightly, weighs, and obtains blackish green carried catalyst, and calculated activity thing content is 18%.
D, the catalyst activation
Get the above-mentioned about 300ml of catalyst for preparing by the C method, put into small-sized solid phase reactor as shown in Figure 2, carefully seal loam cake, accomplish that the ammonia of catalyst decomposes generation can not overflowed immediately.This solid phase reactor is put into as shown in Figure 1 laboratory with high-temperature electric resistance furnace again, made in 5h that temperature is raised to 500 ℃ in the stove, ammonia is empty than being 1: 24 between temperature raising period; Keep 4h under this temperature, control ammonia is empty than being 1: 10 between soak, cools to normal temperature naturally.
E, evaluating catalyst
The catalyst of finishing by the activation of above-mentioned D method is packed in the integral fixedbed reactor of φ a 25 * 600mm carefully, and this reactor is a single tube, external diameter 25mm, internal diameter 21mm, overall height 650mm, catalyst filling volume 120ml, height of bed 400-430mm.This reactor is placed in the molten salt bath, with fused salt conditioned reaction temperature.At 348-350 ℃ of salt temperature, air speed 2000-2300h
-1, benzene concentration 50-54g/M
3Estimate 720h under the condition continuously, the result is benzene conversion ratio 99.3-99.8%, and the cis-butenedioic anhydride weight yield is calculated as 98-102% with 100% purified petroleum benzin.
Embodiment 2:
A, preparing carriers
Prepare carrier by example-1 method A commercial scale, the bulk density 0.61-0.63g/ml of green silicon carbide ring, specific surface (BET method) 0.1-0.2m
2/ g, some pressure laterally 〉=the 2.5kg/ grain, carrier dimensions is external diameter 6.7mm, internal diameter 3.8mm, height 4.5mm.
B, the active matter formulations prepared from solutions
Press example-1 method B preparation, in 380ml water, contain oxalic acid 95.2g, ammonium metavanadate 76.16g, ammonium molybdate 34.52g, nickel nitrate 1.421g, tertiary sodium phosphate 4.954g, neodymium oxide 0.0548g and dysprosium 0.0529g.
C, Preparation of Catalyst
C prepares catalyst by example-1 method, and the quantity that drops into carrier changes 300g into,
D, the catalyst activation
D activates the 300ml catalyst by above-mentioned example-1 method, get the above-mentioned about 300ml of catalyst for preparing by the C method, put into a small-sized solid phase reactor, carefully seal loam cake, accomplish that the ammonia that catalyst decomposes produces can not overflow immediately, again this solid phase reactor is put into laboratory, prevent inside and outside the stove that air from circulating smoothly with high-temperature electric resistance furnace, make in 4h that temperature is raised to 460 ℃ in the stove, ammonia is empty than being 1: 16 between temperature raising period; Keep 4h under this temperature, control ammonia is empty than being 1: 9 between soak, cools to normal temperature naturally.
E, the evaluation of catalyst
Adopt above-mentioned example-1 method E that the catalyst that activated is carried out evaluation test, the benzene conversion ratio is 99.0-99.75% as a result, and the cis-butenedioic anhydride weight yield is for to be calculated as 97-102% with 100% purified petroleum benzin.
Embodiment 3:
A, preparing carriers
Press the carrier compound of example-1, select industrial carrier manufactory to specially invite the green silicon carbide carrier of customization, be of a size of external diameter 7.0mm, internal diameter 3.5mm, height 4.2mm; Bulk density 0.67 ± 0.02g/ml; Specific surface 0.1-0.15m
2/ g, Na in the carrier
2O≤0.3%; Point pressure is only required laterally 〉=the 3kg/ grain.
B, the active matter formulations prepared from solutions
Active matter solution contains oxalic acid 5.3kg according to example-1 preparation in 20.4L water, ammonium molybdate 1.9kg, and ammonium metavanadate 4.2kg adds tertiary sodium phosphate 0.273kg, nickel nitrate 0.79kg, neodymium oxide 3.08g and dysprosium 2.9g with the form of the aqueous solution respectively in addition.
C, Preparation of Catalyst
In the spraying pot of the continuous heating that can constantly rotate, put into the 17.3kg carrier.Prepare the 20kg catalyst by the spraying method of above-mentioned example-1.The active matter load factor is 16 ± 0.5% in the catalyst.
D, the catalyst activation
Is a collection of 18 solid phase reactors that are respectively charged into the catalyst of making as stated above by 20kg, builds loam cake by example-1 requirement.Again these 18 the miniature solid phase reactors of filling catalyst are put into a high-temperature activation stove, make in 4h that temperature is raised to 420 ℃ in the stove, ammonia is empty than being 1: 19 between temperature raising period; Keep 4h under this temperature, control ammonia is empty between soak keeps 2h than being 1: 6 under this temperature, cool to normal temperature naturally.
E, evaluating catalyst
The catalyst that above-mentioned activation is finished carries out the evaluation of continuous 2000h by the E method of example-1, and the result is benzene conversion ratio 99.2-99.7%, and the cis-butenedioic anhydride weight yield is 97-102%.
Embodiment 4:
By activation method of the present invention, the maleic anhydride catalyst 9000kg that industrial production is gone out implements the outer activating process process of novel device by the D method of example-1.
This batch 9000kg catalyst is applied on the 8000t/a benzene preparing cis-butenedioic anhydride by oxidation commercial plant.This reactor is made up of the steel pipe of 11004 φ 25 * 2mm, pipe range 3600mm, every pipe loading height 3300mm, every pipe filling volume 1.14L.This device has moved three months, and reaction condition is: 350 ± 0.5 ℃ of temperature of molten salt, air speed 2200-2300h
-1, benzene concentration 50-53g/NM
3, preceding 3 months result is benzene conversion ratio 98.80-99.40%, the cis-butenedioic anhydride weight yield is calculated as 92-95% by 100% purified petroleum benzin.
Should point out the sensation of the sort of poisoning of impression before personnel's neither one of all participation fillings resembles in this batch catalyst filling process especially.No one's nose is bled or acutely cough.
Claims (7)
1. the outer activation method of the device of a maleic anhydride catalyst is characterized in that: the catalyst of benzene gas phase fixed bed oxidation manufacturing cis-butenedioic anhydride is placed solid phase reactor, again this solid phase reactor is placed high temperature furnace; Process conditions are: soak time 2-10h, guarantees in the space of solid phase reactor that to containing the ammonia air ammonia sky is than being 1: 25-1: 5 by temperature 400-500 ℃.
2. the outer activation method of the device of a kind of maleic anhydride catalyst as claimed in claim 1, the soak time that it is characterized in that described catalyst is 4-9h.
3. the outer activation method of the device of a kind of maleic anhydride catalyst as claimed in claim 1, the activation temperature that it is characterized in that described catalyst is 460-500 ℃.
4. the outer activation method of the device of a kind of maleic anhydride catalyst as claimed in claim 1 is characterized in that described activity of such catalysts component and mol ratio are: V
2O
5: MoO
3: P
2O
5: Na
2O: NiO: Re
2O
3=1: 0.4-0.9: 0.005-0.09: 0.01-0.09: 0.005-0.5: 0.0001-0.002.
5. the outer activation method of the device of a kind of maleic anhydride catalyst as claimed in claim 5 is characterized in that the carrier of described catalyst is the cylinder ring shape, is of a size of: external diameter 6.7-7.0mm, internal diameter 3.5-4.0mm, height 4.0-4.5mm; The Main physical performance indications of carrier: bulk density 0.62-0.70g/ml, the horizontal 2-5kg/ grain of some pressure, vertical 8-20kg/ grain, specific surface 0.08-0.2m
2/ g, Na in the carrier
2The content of O≤0.3%.
6. the outer activation method of the device of a kind of maleic anhydride catalyst as claimed in claim 6 is characterized in that described catalyst carrier is green silicon carbide or alundum (Al.
7. the outer activation method of the device of a kind of maleic anhydride catalyst as claimed in claim 6, it is characterized in that preparing catalyst through hot-spraying technique, at first carrier is put into a rotatable heatable stainless steel rotary drum, constantly rotating under the continuous heating condition, spray to active matter solution on the surface of carrier in the rotary drum by spray gun; Spraying temperature 200-300 ℃, spray time 80-90min; Active matter content is 14-18%.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03130567 CN1272106C (en) | 2003-08-15 | 2003-08-15 | External activating method of cis-butenedioic anhydride catalyst |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03130567 CN1272106C (en) | 2003-08-15 | 2003-08-15 | External activating method of cis-butenedioic anhydride catalyst |
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| Publication Number | Publication Date |
|---|---|
| CN1579631A true CN1579631A (en) | 2005-02-16 |
| CN1272106C CN1272106C (en) | 2006-08-30 |
Family
ID=34578943
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 03130567 Expired - Fee Related CN1272106C (en) | 2003-08-15 | 2003-08-15 | External activating method of cis-butenedioic anhydride catalyst |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102371188A (en) * | 2010-08-27 | 2012-03-14 | 中国石油化工股份有限公司 | Activation furnace for external catalyst activation |
| CN102989494A (en) * | 2012-12-24 | 2013-03-27 | 天津市天环精细化工研究所 | Special benzene-oxidation gas phase fixed-bed catalyst for fumaric acid |
| CN105457686A (en) * | 2015-12-14 | 2016-04-06 | 天津市天环精细化工研究所 | Method for activating benzene-method maleic anhydride catalyst outside reactor |
| CN107774287A (en) * | 2016-08-29 | 2018-03-09 | 中国石油化工股份有限公司 | A kind of loaded catalyst and its preparation for benzene oxidatoin cis-butenedioic anhydride |
| CN107999107A (en) * | 2016-10-28 | 2018-05-08 | 中国石油化工股份有限公司 | A kind of maleic anhydride catalyst and its preparation method and application |
| CN109201095A (en) * | 2017-07-04 | 2019-01-15 | 中国石油化工股份有限公司 | A kind of benzene oxidatoin catalyst for preparing cis-anhydride and the preparation method and application thereof |
| CN110482552A (en) * | 2019-09-04 | 2019-11-22 | 中国科学院山西煤炭化学研究所 | A kind of the activation device and its activation method of super capacitor active carbon |
-
2003
- 2003-08-15 CN CN 03130567 patent/CN1272106C/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102371188A (en) * | 2010-08-27 | 2012-03-14 | 中国石油化工股份有限公司 | Activation furnace for external catalyst activation |
| CN102371188B (en) * | 2010-08-27 | 2013-03-27 | 中国石油化工股份有限公司 | Activation furnace for external catalyst activation |
| CN102989494A (en) * | 2012-12-24 | 2013-03-27 | 天津市天环精细化工研究所 | Special benzene-oxidation gas phase fixed-bed catalyst for fumaric acid |
| CN105457686A (en) * | 2015-12-14 | 2016-04-06 | 天津市天环精细化工研究所 | Method for activating benzene-method maleic anhydride catalyst outside reactor |
| CN107774287A (en) * | 2016-08-29 | 2018-03-09 | 中国石油化工股份有限公司 | A kind of loaded catalyst and its preparation for benzene oxidatoin cis-butenedioic anhydride |
| CN107999107A (en) * | 2016-10-28 | 2018-05-08 | 中国石油化工股份有限公司 | A kind of maleic anhydride catalyst and its preparation method and application |
| CN109201095A (en) * | 2017-07-04 | 2019-01-15 | 中国石油化工股份有限公司 | A kind of benzene oxidatoin catalyst for preparing cis-anhydride and the preparation method and application thereof |
| CN110482552A (en) * | 2019-09-04 | 2019-11-22 | 中国科学院山西煤炭化学研究所 | A kind of the activation device and its activation method of super capacitor active carbon |
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|---|---|
| CN1272106C (en) | 2006-08-30 |
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