CN102962096A - Method for regenerating catalyst for preparing propylene from methanol or dimethyl ether - Google Patents
Method for regenerating catalyst for preparing propylene from methanol or dimethyl ether Download PDFInfo
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Abstract
The invention relates to a method for regenerating a catalyst for preparing propylene from methanol or dimethyl ether. The method comprises the following steps: a, drying the deactivated catalyst for preparing propylene from methanol or dimethyl ether; b, calcining the catalyst in an oxygen-containing regeneration medium at 480-550 DEG C for 4-12h; and c, immersing the calcined catalyst with acid solution, and filtering the acid solution for immersing the catalyst. By optimizing the warming procedure, the formation of non-framework aluminum in the calcining process is reduced, and more acidity activity centers in the catalyst can be kept; and the calcined catalyst is immersed by using the acid solution, so that the deposited carbon in the catalyst can be removed more completely. In comparison with the catalyst regenerated only by using a conventional calcining regeneration method, the catalyst regenerated by the method has the advantages that the catalytic activity is remarkably improved and is almost completely recovered to the reaction activity before inactivation, so that the service life of the catalyst is greatly prolonged.
Description
Technical field
The present invention relates to the renovation process of decaying catalyst in methyl alcohol or dimethyl ether propylene processed, particularly in methyl alcohol or dimethyl ether propylene processed because of the renovation process of the catalyst of carbon deposit and framework aluminum migration inactivation.
Background technology
Traditionally, low-carbon alkene is mainly derived from cracking of oil technique, continuous rise along with International Crude Oil, domestic increasingly soaring to the low-carbon alkene demand, as resources such as the naphtha of ethene, production of propylene raw material, light diesel fuels, be faced with more and more serious short situation, therefore exploitation has great potential and important meaning by the technique (MTP) of methyl alcohol or dimethyl ether production propylene.
Catalyst is the core of coal-based methanol or dimethyl ether propylene technique processed, and at present the main catalyst that uses is HZSM-5 molecular sieve or alkali metal, alkaline-earth metal, the transition metal isoreactivity auxiliary agent of load different content made on the HZSM-5 molecular sieve catalyst.HZSM-5 is a kind of high-silicon type molecular sieve with unique texture, has surface hydrophobicity, for nonpolar molecule very strong adsorption capacity is arranged, and with its uniqueness based on the shape selective of microcellular structure feature and strong acid center and become the three-dimension hole molecular sieve catalyst with acid catalysis and shape selectivity.And the acid site causes carbon deposit easily, causes the obstruction in catalyst surface and the duct, so that catalyst activity and selectivity descends.
The common method of processing at present carbon deposited catalyst is calcining, but catalyst can be emitted a large amount of heat in the process of calcination and regeneration, cause easily catalyst owing to hot-spot and sintering, make on the one hand the catalyst grain size become large, high temperature also can cause framework aluminum to migrate to catalyst surface on the other hand, and the two all can cause catalyst activity to reduce.In addition, the catalyst of carbon deposit still can residual certain carbon deposit in the catalyst when removing carbon deposit by calcining, and this part carbon deposit still is difficult to effective removal with the prolongation of calcination time or the rising of calcining heat.
In the existing relevant regeneration document of catalyst, major part is to use the method for calcination and regeneration, considers how to reduce emphatically the hot-spot problem.The USP4780195 suggestion is added a certain amount of water and is prevented sintering in calcination atmosphere.The method that USP4202865 adopts batch (-type) to annotate oxygen prevents catalyst overheating.USP5037785 adopts the way of Ear Mucosa Treated by He Ne Laser Irradiation to the catalyst decoking under oxygen containing gas.
A kind of cleaning agent that contains monoethanolamine, ether, butanols and phenol is disclosed among the CN1768955A, catalyst to coking deactivation at first cleans, be attached to catalyst surface or build the carbon deposit relatively poor with ability with catalyst to remove part, then carry out calcination and regeneration.Yet this method complicated operation, the cleaning agent cost is high, and is organic easy volatile solvent all, and security is low.CN101584989A provides a kind of renovation process of preparing low carbon olefin hydrocarbon by methanol catalyst system therefor, the method adopts the cleaning agent of organic solvent methyl alcohol, ether, acetone and gasoline preparation, catalyst after soaking inactivation under the ultrasonic condition, can effectively remove the carbon deposit in catalyst surface and the duct, but adopt ultrasound treatment patterns can cause catalyst breakage, and be difficult for realizing large-scale application.
Summary of the invention
In view of this, the object of the present invention is to provide the renovation process of a kind of methyl alcohol or dimethyl ether catalyst for preparing propene, remove thoroughly, affect the problem of regenerated catalyst activity to solve carbon deposit in the existing catalyst regeneration technology.
For achieving the above object, the present invention is by the following technical solutions:
The renovation process of a kind of methyl alcohol or dimethyl ether catalyst for preparing propene comprises:
The methyl alcohol of a, dry inactivation or dimethyl ether catalyst for preparing propene;
B, in containing the oxygen regenerating medium in 480-550 ℃ of calcined catalyst 4-12 hour;
C, the catalyst after will calcining soak in acid solution, then filter out the acid solution that soaks catalyst.
Preferably, described renovation process also comprises steps d, the catalyst after filtering is washed to cleaning solution pH value be not less than 6.5.
Preferably, described renovation process also comprises step e: the product that drying steps c obtains under the condition identical with step a, then under the condition identical with step b, calcine.
Preferably, described renovation process also comprises step f: the product that drying steps d obtains under the condition identical with step a, then under the condition identical with step b, calcine.
Preferably, among the step a with described catalyst at 100-150 ℃ of dry 6-12 hour.
Preferably, the described oxygen regenerating medium that contains is to be selected from least a in the gaseous mixture of nitrogen and air, helium and air, argon gas and air and nitrogen and oxygen; The described molar content that contains oxygen in the oxygen regenerating medium is 1-5%.
Preferably, among the step b, the heating schedule of calcining described catalyst is: the speed with 5-10 ℃/min is warming up to 280-320 ℃ from room temperature, then the speed with 2-4 ℃/min is warming up to 380-420 ℃, constant temperature 2-4h, then the speed with 1-2 ℃/min is warming up to 480-550 ℃, and constant temperature 4-8h finishes.
Preferably, acid solutions described in the step c is 0.5-5mol/L, and soak time is 1-5 hour, and soaking temperature is 30-90 ℃, and described acid solution is a kind of in citric acid, acetic acid or the oxalic acid solution or their combination.
Preferably, in the catalyst after the regeneration carbon content less than 0.5wt%.
Preferably, described catalyst is HZSM-5, SAPO-34 or mordenite molecular sieve catalyst, and perhaps described catalyst is the catalyst of HZSM-5, SAPO-34 or mordenite molecular sieve load.
The catalyst that adopts method regeneration of the present invention to process, can very effectively remove the carbon deposit in the catalyst, and the optimization by calcination procedure, reduced the formation of non-framework aluminum in the calcination process, kept more the acid activated centre in the catalyst, compared with the catalyst that only passes through conventional calcination and regeneration method, catalytic activity significantly improves, almost completely return to the front reactivity of inactivation, thereby greatly prolonged the service life of catalyst.In addition, organic acid of the present invention need not wash after catalyst filters, and can remove fully after the calcining.
Description of drawings
Fig. 1 is the XRD spectra according to catalyst Z 1, Z5, Z11 and the Z12 of embodiment 1,5,7 and 8 preparations;
Fig. 2 is the NH according to catalyst Z 1, Z5, Z11 and the Z12 of embodiment 1,5,7 and 8 preparations
3-TPD spectrogram.
The specific embodiment
The present invention implements by following steps:
Step a, the methyl alcohol of dry inactivation or dimethyl ether catalyst for preparing propene.Preferably, with the catalyst of described inactivation at 100-150 ℃ of dry 6-12 hour; Particularly, can in vacuum drying chamber, carry out drying to decaying catalyst, in drying, vacuumize, reduce in the follow-up calcination process steam to the destruction of catalyst backbone aluminium.
Step b calcined described catalyst 4-12 hour in 480-550 ℃ in containing the oxygen regenerating medium; According to an embodiment of the invention, the described molar content that contains oxygen in the oxygen regenerating medium is 1-5%, and the described oxygen regenerating medium that contains can be any suitable gas with oxygen in the above-mentioned scope.Instantiation can be at least a in the gaseous mixture that is selected from nitrogen and air, helium and air, argon gas and air and nitrogen and oxygen.One skilled in the art will appreciate that the oxygen content that contains in the oxygen regenerating medium can regulate according to reaction bed temperature in the roasting, to avoid the catalyst permanent deactivation that excess Temperature causes in the roasting.Oxygen content and regulate and control method thereof can adopt the conventional method in this field, are not described in detail in this.
According to an embodiment of the invention, in step b, preferably, the heating schedule of calcining described catalyst is: the speed with 5-10 ℃/min is warming up to 280-320 ℃ from room temperature, then the speed with 2-4 ℃/min is warming up to 380-420 ℃, constant temperature 2-4h, then the speed with 1-2 ℃/min is warming up to 480-550 ℃, and constant temperature 4-8h finishes.Catalyst calcination also can cause framework aluminum to migrate to catalyst surface, catalyst activity is reduced, roasting process can cause the migration of framework of molecular sieve aluminium, variation has occured in the coordination structure that mainly is aluminium, and wherein framework aluminum has four coordination structures, and non-framework aluminum has six coordination structures, the variation of coordination structure and the temperature of roasting and heating rate have relation, temperature is higher, the easier polymerization of framework aluminum and migration occurs form non-framework aluminum, and the difference of heating rate also can cause different results.Therefore, the heating schedule by the optimization of catalysts calcining can effectively reduce the migration of framework aluminum.
Step c soaks the catalyst after the calcining with acid solution, then filter out the acid solution that soaks catalyst, to obtain catalyst.According to an embodiment of the invention, described acid solutions is 0.5-5mol/L, and soak time is 1-5 hour, and soaking temperature is 30-90 ℃, and preferred described acid solutions is 1-3mol/L; If acid solutions is excessively low, can affect exchange efficiency; If acid solutions is too high, can destroy the structure of framework aluminum, affect catalytic activity.Described acid solution and the non-framework aluminum reaction of calcining in the rear catalyst, the carbon deposit to be difficult to get rid of by calcining in non-framework aluminum in the Removal of catalyst and the non-framework aluminum kills two birds with one stone so that in the catalyst after the regeneration carbon content less than 0.5wt%; And after the acid solution immersion, the crystalline structure of described catalyst does not change.
Preferably, described acid solution is a kind of or combination in citric acid, acetic acid or the oxalic acid solution.Above-mentioned organic acid can wash at the filtration rear catalyst except having stronger acidity, and described organic acid can be removed in calcination process fully, and cost is low, and is simple to operate and nontoxic.
In an embodiment of the invention, renovation process of the present invention also comprises steps d: the catalyst that step c is obtained washs to cleaning solution pH value and is not less than 6.5, to reduce residual in catalyst of acid solution, particularly when containing in the acid solution when calcining the material that to remove fully.
In yet another embodiment of the present invention, renovation process of the present invention also further comprises step: the product that drying steps c or steps d obtain under the condition identical with step a, then under the condition identical with step b, calcine.
In addition, renovation process of the present invention is particularly useful for HZSM-5, SAPO-34 or mordenite molecular sieve catalyst, and those skilled in the art are easy to expect, and is applicable too for the catalyst of HZSM-5, SAPO-34 or mordenite molecular sieve load.
The invention will be further elaborated by embodiment below in conjunction with accompanying drawing, but obvious scope of the present invention is not limited in following examples.
Embodiment 1
Get the HZSM-5 molecular sieve catalyst (MTPROP-1, Germany south chemistry) of coking deactivation, be placed in the vacuum drying chamber in 120 ℃ of dryings 6 hours; Dried catalyst is warming up to 550 ℃ in Muffle furnace, and is roasting under 1% the atmosphere in oxygen content.The heating schedule of described Muffle furnace is: the speed with 5 ℃/min is warming up to 300 ℃ from room temperature, be warming up to 400 ℃ with the speed of 2 ℃/min from 300 ℃, constant temperature 2h is warming up to 550 ℃ with the speed of 1 ℃/min from 400 ℃, constant temperature 6h finishes, and the catalyst that obtains is designated as Z1.
Embodiment 2
Place vacuum drying chamber in 150 ℃ of dryings 6 hours the HZSM-5 molecular sieve catalyst of coking deactivation; Dried catalyst is warming up to 550 ℃ in Muffle furnace, and is roasting under 5% the atmosphere in oxygen content.The heating schedule of described Muffle furnace is: the speed with 10 ℃/min is warming up to 300 ℃ from room temperature, be warming up to 400 ℃ with the speed of 4 ℃/min from 300 ℃, constant temperature 2h is warming up to 550 ℃ with the speed of 2 ℃/min from 400 ℃, constant temperature 4h finishes, and the catalyst that obtains is designated as Z2.
Embodiment 3
Place vacuum drying chamber in 100 ℃ of dryings 8 hours the HZSM-5 molecular sieve catalyst of coking deactivation; Dried catalyst is warming up to 550 ℃ in Muffle furnace, and is roasting under 2% the atmosphere in oxygen content.The heating schedule of described Muffle furnace is: the speed with 5 ℃/min is warming up to 480 ℃ from room temperature, and constant temperature 12h finishes, and the catalyst that obtains is designated as Z3.
Embodiment 4
Place vacuum drying chamber in 120 ℃ of dryings 6 hours the HZSM-5 molecular sieve catalyst of coking deactivation; Dried catalyst is warming up to 550 ℃ in Muffle furnace, and is roasting under 5% the atmosphere in oxygen content.The heating schedule of described Muffle furnace is: the speed with 10 ℃/min is warming up to 550 ℃ from room temperature, and constant temperature 4h finishes, and the catalyst that obtains is designated as Z4.
Embodiment 5
Catalyst Z 1 is put into 90 ℃, 0.5mol/L citric acid solution to be soaked 5 hours.After the filtration with catalyst in 100 ℃ of dryings 12 hours, then roasting 6 hours under the atmosphere of 480 ℃ and oxygen content 2% in Muffle furnace, the catalyst that obtains is designated as Z5.
Embodiment 6
Catalyst Z 2 is put into 50 ℃, 5mol/L citric acid solution to be soaked 1 hour.After the filtration with catalyst in 120 ℃ of dryings 8 hours, then roasting 6 hours under the atmosphere of 480 ℃ and oxygen content 2% in Muffle furnace, the catalyst that obtains is designated as Z6.
Embodiment 7
Get the SAPO-34 molecular sieve catalyst (Shanghai Zhuoyue Chemical Science Co., Ltd) of coking deactivation, be placed in the vacuum drying chamber in 120 ℃ of dryings 6 hours; Dried catalyst is warming up to 550 ℃ in Muffle furnace, and is roasting under 1% the atmosphere in oxygen content.The heating schedule of described Muffle furnace is: the speed with 5 ℃/min is warming up to 320 ℃ from room temperature, be warming up to 420 ℃ with the speed of 2 ℃/min from 320 ℃, constant temperature 2h is warming up to 480 ℃ with the speed of 1 ℃/min from 420 ℃, constant temperature 8h finishes, and the catalyst that obtains is designated as Z7.
Embodiment 8
Catalyst Z 7 is put into 30 ℃, 3mol/L acetic acid solution to be soaked 5 hours.After the filtration with catalyst in 100 ℃ of dryings 12 hours, then roasting 8 hours under the atmosphere of 480 ℃ and oxygen content 1% in Muffle furnace, the catalyst that obtains is designated as Z8.
Embodiment 9
Get the mordenite molecular sieve catalyst (Shanghai zeolite molecular sieve Co., Ltd) of coking deactivation, place vacuum drying chamber in 150 ℃ of dryings 6 hours; Dried catalyst is warming up to 550 ℃ in Muffle furnace, and is roasting under 5% the atmosphere in oxygen content.The heating schedule of described Muffle furnace is: the speed with 8 ℃/min is warming up to 280 ℃ from room temperature, be warming up to 380 ℃ with the speed of 2 ℃/min from 280 ℃, constant temperature 4h is warming up to 530 ℃ with the speed of 2 ℃/min from 380 ℃, constant temperature 8h finishes, and the catalyst that obtains is designated as Z9.
Embodiment 10
Catalyst Z 9 is put into 50 ℃, 4mol/L oxalic acid solution to be soaked 5 hours.After the filtration with catalyst in 100 ℃ of dryings 12 hours, then roasting 6 hours under the atmosphere of 480 ℃ and oxygen content 2% in Muffle furnace, the catalyst that obtains is designated as Z10.
Comparative Examples 1
The HZSM-5 catalyst of getting coking deactivation is designated as Z11, gets fresh HZSM-5 catalyst and is designated as Z12.
Adopt QL-HW2000B infrared carbon sulfur analyzer (Qilin Analytical Instrument Co., Ltd., Nanjing) that the carbon deposit content in the catalyst is measured.Measurement result sees Table 1.
Carbon content in table 1 catalyst
| Catalyst | Carbon deposit content (wt%) |
| Z1 | 2.15 |
| Z2 | 2.24 |
| Z5 | 0.43 |
| Z6 | 0.52 |
| Z7 | 2.17 |
| Z8 | 0.37 |
| Z9 | 2.20 |
| Z10 | 0.42 |
| Z11 | 15.38 |
Contrast as seen, the carbon deposit content among Z1 and the Z2 is significantly less than the carbon deposit content of Z11, illustrates through effectively having reduced the carbon deposit in the decaying catalyst after the calcining; Find by analyzing, after the calcining, still have the part carbon deposit to be difficult to remove in the catalyst, and the carbon deposit content among Z5, Z6, Z8 and the Z10 illustrate after peracid solutions is soaked and has further removed the carbon deposit in the catalyst respectively further less than the carbon deposit content of Z1, Z2, Z7 and Z9.
Adopt system400 magnetic nuclear resonance analyzer (German BRUKER company) that Z1, Z2, Z3, Z4, Z7 and Z9 are detected, to measure framework aluminum and the non-framework aluminum content in the molecular sieve, see Table 2, wherein non-framework aluminum is moved to molecular sieve surface and is formed from framework aluminum.
Table 2 decaying catalyst is through calcining back skeleton aluminium and non-framework aluminum content
| Catalyst | Framework aluminum content (%) | Non-framework aluminum content (%) |
| Z1 | 42.0 | 3.0 |
| Z2 | 41.8 | 3.2 |
| Z3 | 40.0 | 5.0 |
| Z4 | 37.8 | 7.2 |
| Z7 | 50.2 | 4.5 |
| Z9 | 45.5 | 4.7 |
By as seen from Table 2, by the control to calcination process, can effectively reduce the generation of non-framework aluminum.
SHIMADZU Lab XRD-6000 type X-ray diffraction (XRD) instrument that adopts Japanese Shimadzu company to produce is measured above-mentioned catalyst Z 1, Z5, Z11 and Z12 respectively.Wherein pipe is pressed 40kv, tube current 30mA, and CuK α radiation, sweep limits 2 θ: 5～90 °, sweep speed is 4 °/min.The result as shown in Figure 1.Referring to Fig. 1, lattice damage does not occur with further consistent with the crystalline structure of fresh catalyst Z12 through the catalyst of peracid solutions processing in the catalyst Z 1 after the calcining, and this is the basis that can recover through regeneration catalyst activity.
Adopt Tianjin to weigh first the NH that company's T P5000 type chemical adsorption instrument carries out Z1, Z5, Z11 and Z12
3-TPD acid characterization as shown in Figure 2, can be found out, acidity of catalyst by by force to a little less than be followed successively by: fresh catalyst Z12〉acid treatment catalyst Z 5 calcining rear catalyst Z1 decaying catalyst Z11, calcining only can recover acidity to a certain degree, and after peracid treatment, acidity can better be recovered.
Catalyst breakage is become the 40-60 order, adopts Shanghai China to like that the GC-9560 gas-chromatography that chromatographic apparatus company produces carries out on-line analysis at micro anti-evaluation device (river petrochemical industry Science and Technology Ltd. is opened up in Beijing), react 72 hours the results are shown in Table 3.Reaction condition: reaction temperature is 480 ℃, and reaction pressure is normal pressure, and the feed rate of material benzenemethanol is 5g/h, and the feed rate of raw water is 2.5g/h.
Table 3 adopts the product of the preparing propylene from methanol reaction of different catalysts to distribute
| Catalyst | Methanol conversion | Ethene | Propylene |
| Z11 | 21.37% | 0.56% | 2.33% |
| Z12 | 99.50% | 12.38% | 40.98% |
| Z1 | 65.72% | 2.02% | 21.35% |
| Z2 | 65.52% | 2.03% | 21.28% |
| Z3 | 63.86% | 2.01% | 21.15% |
| Z4 | 64.22% | 2.01% | 21.18% |
| Z5 | 98.96% | 11.78% | 39.69% |
| Z6 | 99.03% | 12.11% | 39.25% |
| Z8 | 99.42% | 39.70% | 41.36% |
| Z10 | 99.15% | 20.84% | 28.13% |
The catalytic activity of regenerated catalyst characterizes with methanol conversion:
The quantity of methyl alcohol of methanol conversion=conversion/methyl alcohol initial amount.
Compare with the catalyst Z 11 of inactivation, the methyl alcohol reaction result of Z1 and Z2 shows: only the activity through a rear catalyst of roasting regeneration significantly improves, but catalytic activity is lower (＜70%) still, through for the second time regeneration (with the first time regeneration condition identical) after, the activity of catalyst is still without improve.Show that simple roasting is difficult to recover fully the activity of catalyst.And the catalyst of roasting under different Elevated Temperature Conditions, because the non-framework aluminum content that generates is different, the catalyst activity of Z1 and Z2 is compared also with Z4 with Z3 and is improved.In addition, after the peracid solutions immersion treatment, catalyst Z 5, Z6, Z8 and Z10 almost completely return to the reactivity before the inactivation, thereby have greatly prolonged the service life of catalyst, have further reduced production cost.
Although described embodiments of the present invention by preferred embodiment, but one skilled in the art should appreciate that, can change in these embodiments and do not deviate from principle of the present invention and spirit, scope of the present invention is limited by claim and equivalent thereof.
Claims (10)
1. the renovation process of a methyl alcohol or dimethyl ether catalyst for preparing propene comprises:
The methyl alcohol of a, dry inactivation or dimethyl ether catalyst for preparing propene;
B, in containing the oxygen regenerating medium in 480-550 ℃ of calcined catalyst 4-12 hour;
C, the catalyst after will calcining soak in acid solution, then filter out the acid solution that soaks catalyst.
2. renovation process as claimed in claim 1 is characterized in that, described renovation process also comprises steps d: the catalyst after filtering is washed to cleaning solution pH value be not less than 6.5.
3. renovation process as claimed in claim 1 is characterized in that, described renovation process also comprises step e: the product that drying steps c obtains under the condition identical with step a, then under the condition identical with step b, calcine.
4. renovation process as claimed in claim 2 is characterized in that, described renovation process also comprises step f: the product that drying steps d obtains under the condition identical with step a, then under the condition identical with step b, calcine.
5. such as each described renovation process among the claim 1-4, it is characterized in that, among the step a with described catalyst at 100-150 ℃ of dry 6-12 hour.
6. renovation process as claimed in claim 1 is characterized in that, the described oxygen regenerating medium that contains is to be selected from least a in the gaseous mixture of nitrogen and air, helium and air, argon gas and air and nitrogen and oxygen; The described molar content that contains oxygen in the oxygen regenerating medium is 1-5%.
7. such as each described renovation process among the claim 1-4, it is characterized in that, among the step b, the heating schedule of calcining described catalyst is: the speed with 5-10 ℃/min is warming up to 280-320 ℃ from room temperature, then the speed with 2-4 ℃/min is warming up to 380-420 ℃, constant temperature 2-4h, then the speed with 1-2 ℃/min is warming up to 480-550 ℃, and constant temperature 4-8h finishes.
8. renovation process as claimed in claim 1, it is characterized in that acid solutions described in the step c is 0.5-5mol/L, soak time is 1-5 hour, soaking temperature is 30-90 ℃, and described acid solution is a kind of in citric acid, acetic acid or the oxalic acid solution or their combination.
9. renovation process as claimed in claim 1 is characterized in that, carbon content is less than 0.5wt% in the catalyst after the regeneration.
10. such as claim 1 or 9 described renovation process, it is characterized in that described catalyst is HZSM-5, SAPO-34 or mordenite molecular sieve catalyst, perhaps described catalyst is the catalyst of HZSM-5, SAPO-34 or mordenite molecular sieve load.
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