CN106944137B - The utilization method of useless hydrogenation catalyst - Google Patents
The utilization method of useless hydrogenation catalyst Download PDFInfo
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- CN106944137B CN106944137B CN201610003157.9A CN201610003157A CN106944137B CN 106944137 B CN106944137 B CN 106944137B CN 201610003157 A CN201610003157 A CN 201610003157A CN 106944137 B CN106944137 B CN 106944137B
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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
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- 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
- Y02P20/584—Recycling of catalysts
Abstract
The invention discloses a kind of utilization methods of useless hydrogenation catalyst.This method comprises: being impregnated after useless hydrogenation catalyst is ground using ammonium hydroxide, aluminium oxide, binder and acid solution are then added in remaining solid and carries out kneading and compacting；Then in a high pressure reaction kettle, reduction treatment is carried out to it using hydrogen；Polyalcohol and/or furfuryl aldehyde solution are added in autoclave, hydrogenation reaction is carried out；Dry materials after reaction until surface without liquid phase, then after successively contact with organic acid, ammonium or ammonia, carried heteropoly acid, obtained catalyst for ethanol delydration to ethylene.Hydrogenation active metal component and carrier component in useless hydrogenation catalyst is not only utilized in this method, and take full advantage of the hydrogenation activity of useless hydrogenation catalyst, improve the utilization rate of dead catalyst, solve the pollution problem of dead catalyst, and the function admirable of resulting catalyst for ethanol delydration to ethylene.
Description
Technical field
The present invention relates to a kind of utilization methods of useless hydrogenation catalyst, are especially prepared by waste residue oil hydrogenating treatment catalyst
The method of catalyst for ethanol delydration to ethylene.
Background technique
The annual whole world, which will generate, can not largely carry out regenerated dead catalyst, and wherein hydrogenation catalyst occupies phase
When big specific gravity.Catalyst for hydrotreatment of residual oil service life is short, and is lost due to the deposition of the impurity such as a large amount of W metals and V
It can not be regenerated after work, especially in waste residue oil Hydrobon catalyst, molybdenum, cobalt, the nickel etc. that are 20wt%~40wt% containing total amount
Metal values oxide, if by these dead catalyst abandon or as building etc. industries filler, not only result in resource
Waste, and since the loss of metal causes certain pollution to environment, it is especially more serious to water resource pollution.Recently, ring
Regulation is protected to be increasingly stringenter the discarding of dead catalyst.Useless hydrogenation catalyst is considered by U.S. environment protection mechanism (USEPA)
Danger wastes.
The processing technique of dead catalyst is specifically included that and is 1. burned at present, is 2. milled, 3. oxidizing roasting, and 4. alkaline leaching returns
Molybdenum, vanadium are received, 5. acidic leaching Call Provision, nickel, 6. waste sludge discharge etc..Metal in recycling dead catalyst is a kind of preferable choosing
It selects, can not only economize on resources, but also can reduce environmental pollution.But existing dead catalyst metal recovery technology is generally existing
Some problems: the valuable metal recoveries such as vanadium, molybdenum, cobalt, nickel are incomplete, and some only recycles one such or two kinds；The rate of recovery compared with
Low, the usual rate of recovery only has the % of 70 %~80.Metal recovery processes are one for the catalyst having had no value for use really
The preferable selection of kind, but its own benefit is not obvious.Especially in China, due to the price phase of hydrogenation catalyst carried metal
To relatively cheap, thus extracted from useless hydrogenation catalyst recycling metal in addition to environmental benefit preferably other than, economic benefit is simultaneously unknown
It is aobvious.It is raw material to generate other value products be an ideal using dead catalyst so from environment and economic viewpoint
Selection.
Useless hydrogenation catalyst is also commonly used for preparing new hydrogenation catalyst, but usually slop cut oil hydrogenation catalysts.
For example US4888316 is to grind useless Hydrobon catalyst, adds salic material, is formed, is made charcoal etc. and is processed
Journey obtains the Hydrobon catalyst that can be continued to use.CN1552521A is added into useless Hydrobon catalyst powder
Then a small amount of active metal component regenerates, obtain new Hydrobon catalyst.The above method is to useless Hydrobon catalyst
Partial change very little, and according to the catalyst of the new same purposes of the purposes of dead catalyst preparation, pass through increased portion load sharing
The mode of body or active metal, the raising of catalyst comprehensive performance largely still rely on the performance of original catalyst.It is useless
Catalyst for hydrotreatment of residual oil covers catalyst surface, makes number of active center due to being wherein deposited with a large amount of metal impurities
Reduction or blocking catalyst aperture, hinder the utilization of inner surface, and catalyst is difficult to be used in by regenerating activity recovery
New hydrogenation catalyst is prepared, can also be made a big impact to catalyst performance, its rapid deactivation is caused.
Some hydrotreaters for requiring high activity and catalysts selective, after catalyst inactivation (or by regeneration)
It is suitble to the device of other lower requirements to use.When hydrotreating catalyst with use its is active, selectivity constantly decline so that
It is not available in the hydrotreater of other low requirements yet, it is still it is contemplated that it is sharp again on certain non-hydrogenation plants
With.CN1354039A describes a kind of method for preparing catalyst of selective catalytic reduction for nitrogen oxide, which is
It is prepared using the dead catalyst that the hydrodesulfurization of oil plant is discharged, there is excellent nitrogen oxide selective removal effect
And it is better protected from the catalyst poisoning generated to sulfur oxide.CN1359751A describes a kind of for removing urging for dioxin
Agent and preparation method thereof, the dead catalyst preparation which is discharged by regeneration from oil plant hydro desulfurization, has excellent
It is good to remove dioxin performance and lower due to having regenerated dead catalyst its preparation cost.USP20050075528A1 describes one
Kind uses the technique of sulphur, nitrogen, aromatic hydrocarbons in dead catalyst adsorbing and removing oil product, which uses NiMo/Al2O3And CoMo/Al2O3
Type hydrodesulfurization dead catalyst oil purification does not have to specially treated using preceding, heating is not had to when use.
Flagship product of the ethylene as basic Organic Chemicals and petro chemical industry, about 75% chemical products
It is to be prepared by raw material of ethylene.In recent years, ethyl alcohol especially recyclable organism preparing ethylene by dehydrating ethanol increasingly by
To the attention of people, it is various to have the advantages that green, sustainable, reaction condition is mild and product ethylene is with high purity etc.,
With the part or all of great potential for replacing obtaining ethylene from petroleum.There are many catalyst for ethanol delydration to ethylene report, mainly
It is activated alumina, molecular sieve and heteropoly acid etc..
Li Benxiang etc. [Chemical Engineering Technology and exploitation, 2010,5 (39): 7-9] reports entitled MCM-41 load Catalyzed by Silicotungstic Acid
The article of producing ethylene from dehydration of ethanol, catalyst are prepared using infusion process.CN200910057539.X discloses a kind of ethanol dehydration
The catalyst of ethylene processed.For the catalyst using aluminium oxide as carrier, active component is heteropoly acid, is prepared using kneading method.It is above-mentioned to urge
Agent shows higher catalytic activity and selectivity when using high concentration ethanol as raw material, but working as with low-concentration ethanol is original
When material, catalyst activity is decreased obviously, and stability is bad.
Summary of the invention
Place in order to overcome the shortcomings in the prior art, the present invention provides a kind of utilization methods of useless hydrogenation catalyst.
This method prepares catalyst for ethanol delydration to ethylene using useless hydrogenation catalyst.This method is not only utilized in useless hydrogenation catalyst
Hydrogenation active metal component and carrier component, and the hydrogenation activity of useless hydrogenation catalyst is taken full advantage of, solve useless catalysis
The pollution problem of agent, and economize on resources, improve benefit, it is technically easy to implement, resulting producing ethylene from dehydration of ethanol catalysis
The function admirable of agent.
The utilization method of the useless hydrogenation catalyst, i.e., useless hydrogenation catalyst prepare catalyst for ethanol delydration to ethylene
Method, comprising:
(1) pretreated useless hydrogenation catalyst is ground；
(2) dead catalyst powder will be obtained in step (1) and be added in ammonium hydroxide to impregnate, then filter, it is insoluble to obtain solid
Object；
(3) after drying by the solid insoluble in step (2), aluminium oxide, binder, acid solution kneading and compacting is added,
Through dry and roasting, catalyst precarsor A is obtained；
(4) the resulting catalyst precarsor A of step (3) is added in autoclave, it is restored using hydrogen
Processing；
(5) polyalcohol and/or furfuryl aldehyde solution are driven into autoclave, then adjusting Hydrogen Vapor Pressure to 2 MPa ~ 4MPa,
0.5h ~ 5.0h is reacted at 100 DEG C ~ 300 DEG C；
(6) after filtering by the material after reaction in step (5), it is dried at room temperature, until sample surfaces aneroid
Phase obtains catalyst precarsor B；
(7) the catalyst precarsor B that step (6) obtains being added in aqueous solutions of organic acids, heating stirring to solution is evaporated,
Obtain catalyst precarsor C；
(8) the catalyst precarsor C that step (7) obtains is added in the alkaline solution containing ammonium, through filtering, 40 DEG C ~ 90
It is dry at DEG C；Or the catalyst precarsor C that step (7) obtains is adsorbed into ammonia at 40 DEG C ~ 90 DEG C, obtain catalyst precarsor D；
(9) aqueous solution of heteropoly acid is added in the catalyst precarsor D that step (8) obtains, heating stirring to solution is steamed
It is dry, to get catalyst for ethanol delydration to ethylene after drying and roasting.
The useless hydrogenation catalyst can be the discarded hydrogenation catalyst in any source, generally with group VIB and/or
Group VIII metal is active metal component, alumina-based supports, for example former reaction has been not achieved and has required, or due to gradation
Reason is de- without the catalyst for hydrotreatment of residual oil used in the fixed bed or ebullated bed of complete deactivation, especially residual hydrogenation
Sulfur catalyst, hydrotransforming catalyst for residual oil etc..Wherein give up hydrogenation catalyst preferably comprise active metal Ni, in terms of oxide
1wt% or more, preferably 3wt% or more.Other active metal components such as Co can also be contained in the dead catalyst, may be used also
To contain one of adjuvant component, such as titanium, boron, silicon etc. or a variety of, preferably silicon.On the basis of the weight of carrier, silica
Content is 8% ~ 18%.The waste residue oil hydrogenating treatment catalyst generally has the deposition of the impurity such as part metals Ni and V.
In step (1), the pretreatment for the hydrogenation catalyst that gives up can use solvent extraction process, then through dry and roasting.One
As the solvent that uses can be one of petroleum ether, toluene or a variety of.Dry and roasting condition is as follows: doing at 80 DEG C ~ 120 DEG C
Dry 5h ~ 12h roasts 2h ~ 6h at 400 DEG C ~ 700 DEG C.
The hydrogenation catalyst that gives up in step (1) is ground to more than 200 mesh.
The concentration of ammonia spirit described in step (2) is generally 20wt%~40wt%, soaking process need to stir and
Heating, the h of soaking time 2h ~ 8, temperature is at 40 DEG C ~ 80 DEG C.
Step (2) is the Mo and V removed in dead catalyst with the main purpose that ammonium hydroxide impregnates, and is retained on dead catalyst
Ni and carrier component such as aluminium oxide etc..
In step (3), the dry condition of solid insoluble is as follows: in 90 DEG C ~ 120 DEG C drying 3 h ~ 12 h.
In step (3), after molding, dry and roasting condition is as follows: in 90 DEG C ~ 120 DEG C drying h of 3 h ~ 12, then existing
300 DEG C ~ 600 DEG C roasting 2 h ~ 6 h.
In step (3), the aluminium oxide aluminium oxide and its its precursor used when being conventional carrier preparation, aluminium oxide
Additional amount accounts for 5wt%~40wt% of drying solid insoluble matter weight.
In step (3), acid solution is dilute acid soln, acid can selected from hydrochloric acid, sulfuric acid, nitric acid, citric acid, acetic acid, phosphoric acid,
The one or more of boric acid, preferably hydrochloric acid or nitric acid；The concentration of acid solution is generally 0.2 ~ 5.0 mol/L.The acid of addition is molten
Liquid is 3wt% ~ 15wt% of drying solid insoluble matter weight.
In step (4), the reduction treatment process is as follows: under hydrogen atmosphere by catalyst precarsor be warming up to 300 DEG C~
600 DEG C, after handling 4h~8h at 0.1MPa~0.5MPa, it is down to reaction temperature.Wherein reduction treatment can use pure hydrogen,
The hydrogen containing inert gas can also be used, hydrogen volume concentration is 30% ~ 100%.
In step (5), the polyalcohol is one of C5~C10 polyalcohol or a variety of, preferably xylitol, sorb
One of alcohol, mannitol, arabite are a variety of；The mass concentration of polyalcohol and/or furfuryl aldehyde solution is 5%~35%, preferably
It is 5%~30%.The mass ratio of the additional amount of polyalcohol and/or furfural and catalyst precarsor A are 2:1 ~ 10:1, preferably 3:1 ~
10:1。
In step (7), the organic acid is one of citric acid, tartaric acid, malic acid or a variety of.The organic acid
Account for the 10%~70% of catalyst precarsor A weight.
In step (8), the catalyst precarsor B that step (7) obtains is added in the alkaline solution containing ammonium and is impregnated, soaked
The stain time is generally the min of 5 min ~ 30.The catalyst precarsor B that step (7) is obtained adsorbs ammonia, and adsorption time is generally 5
min~30 min.In step (8), the alkaline solution containing ammonium is ammonium hydroxide, sal volatile, one in ammonium bicarbonate soln
Kind is a variety of.
In step (8), pure ammonia is can be used in the ammonia, the gaseous mixture containing ammonia can also be used, in mixed gas
It is other for one of inert gas such as nitrogen, argon gas etc. or a variety of in addition to ammonia.
In step (9), the heteropoly acid is one of phosphotungstic acid, silico-tungstic acid, phosphomolybdic acid or a variety of.
In step (7) or step (9), the heating stirring is generally carried out at 40 DEG C ~ 90 DEG C.
Drying described in step (9) and roasting condition are as follows: in 90 DEG C ~ 120 DEG C drying h of 3 h ~ 12, then 300 DEG C ~
550 DEG C of roasting 2 h ~ 6 h.
In step (9) resulting catalyst for ethanol delydration to ethylene, the content of ammonium heteropoly acids is 5% ~ 25%, preferably 8%
~20%；Wherein ammonium heteropoly acids are shown in formula (1)；
Hm(NH4)nYX12O40(1)
Wherein X represents W or Mo, and Y represents Si or P；When Y represents Si, m+n=4, n value is 0.1 ~ 1.0；When Y represents P
When, m+n=3, n value is 0.1 ~ 1.0.
In the catalyst as made from the method for the present invention, ammonium heteropoly acids are distributed in the outer surface of dead catalyst.
In step (9) resulting catalyst for ethanol delydration to ethylene, preferably NiO content is 3% ~ 6%.
It in the method for the present invention, also can according to need, suitably supplement nickel, nickel can be loaded to using conventional carrying method
It on the resulting catalyst precarsor A of step (3), can also be added in the kneading process of step (3), for example use infusion process, leaching
After stain, need as follows by dry and roasting, the drying and roasting condition: in 90 DEG C ~ 120 DEG C drying h of 3 h ~ 12,
Then in 300 DEG C ~ 550 DEG C roasting 2 h ~ 6 h.Nickel source is one of nickel nitrate, nickel acetate or a variety of.
The present invention also provides a kind of methods of producing ethylene from dehydration of ethanol, wherein using catalyst of the invention.The present invention
Catalyst is ethylene reaction produced especially suitable for low-concentration ethanol raw material dehydration.The concentration of the ethanol raw material be 5wt% ~
30wt%.In the present invention, the reaction condition of producing ethylene from dehydration of ethanol is as follows: 0.5 h of mass space velocity-1~12 h-1, reaction temperature 280
℃~400 ℃。
Method of the invention compared with prior art, has the following advantages that and feature:
1, physical property (specific surface, Kong Rong and aperture) and mechanical property requirements of the method for the present invention to useless hydrogenation catalyst
It is lower, former reaction requirement is not achieved especially suitable for recycling, or without complete deactivation due to gradation
The catalyst for hydrotreatment of residual oil used in fixed bed or ebullated bed.
2, the present invention impregnates dead catalyst by ammonia spirit, is dissolved in Mo and V in useless hydrogenation catalyst in solution, makes
Its recycling that can carry out other purposes, improves the utilization rate of dead catalyst.
3, the method for the present invention improves the pore structure of catalyst by the way that aluminium oxide is added into useless hydrogenation catalyst powder, together
When acid solution is added, thus it is possible to vary the dispersion of supported metal, and improve the pore structure of catalyst.
4, the method for the present invention takes full advantage of the active metal component in useless hydrogenation catalyst, serves not only as ethanol dehydration
The auxiliary agent of catalyst for ethylene, and hydrogenation is played in polyalcohol and/or furfural liquid-phase hydrogenatin reaction；Simultaneously also sufficiently
The carrier component of dead catalyst is utilized, realizes the comprehensive utilization of metal and carrier, improves resource utilization, has saved big
Measure cost.
5, catalytic polyol and/or furfural liquid-phase hydrogenatin in autoclave using useless hydrogenation catalyst generates liquid alkane,
It is adsorbed on catalyst precarsor A, can effectively block the duct of catalyst precarsor A, and during the reaction before catalyst
It is generated on body A carbon distribution (in subsequent roasting process can burn off), the acidity of catalyst precarsor A can be weakened to a certain extent,
The quantity for reducing acidic site absorption ammonia, makes heteropoly acid mainly react with ammonium salt organic acid and generates ammonium heteropoly acids, facilitate
Ammonium heteropoly acids are evenly dispersed on useless hydrogenation catalyst surface, avoid assembling, and can remove through subsequent high-temperature roasting
Above-mentioned carbon deposit effectively remains this Component Vectors acidic site in this way.The catalyst of this method preparation not only has low temperature active
It is high, selectivity is good, the characteristics of having strong anti-carbon capacity, and stability is good.
6, present invention process technology is novel, and reasonable flowsheet structure, method is simple, and operation easy to implement, low energy consumption.
Specific embodiment
The solution of the present invention and effect are further illustrated below by specific embodiment.In the present invention, wt% is quality point
Number.
Embodiment 1
(1) preparation of catalyst precarsor A, steps are as follows:
The useless Hydrobon catalyst for selecting fixed bed residual hydrogenation commercial plant extracts 40h using petroleum ether solvent,
Dry 8h, roasts 3h at 600 DEG C at 110 DEG C, and pretreated dead catalyst is made (containing MoO3: 11.0 wt%, NiO:
5.7 wt%, V2O5: 3.0 wt%, Al2O3: 69.0 wt%, SiO2: 10.3 wt%).Catalyst is ground to 200 mesh and (refers to by 200
Mesh), 200 grams of powder weight are weighed, 400 mL of ammonium hydroxide that concentration is 25 wt% is added, 6 h, mistake are impregnated in stirring at 60 DEG C
Filter obtains filtrate A and solid insoluble B, by solid insoluble B in 110 DEG C of dry 8h, then weighs 100 grams of powder weight, adds
Enter 850 DEG C roasting after 19 grams of aluminium oxide, be added 1.0mol/L nitric acid solution 42mL, after mixing on banded extruder extrusion at
In 110 DEG C of dry 8h, then in 400 DEG C of roasting 3h, catalyst precarsor A is made in type.
(2) preparation of catalyst, steps are as follows:
90g catalyst precarsor A is added in autoclave, 450 DEG C are warming up under hydrogen atmosphere, at 0.3MPa
4h is handled, reaction temperature is down to, the sorbitol solution that 400g mass concentration is 20% is added, then adjusting Hydrogen Vapor Pressure to 3MPa,
3h is reacted at 260 DEG C, after reaction, catalyst filtration is come out, and is dried at room temperature to carrier surface without liquid phase；Then plus
Enter into the aqueous solution containing 21.3g citric acid, stirring to solution is evaporated at 40 DEG C；It is molten that obtained material is added to ammonium carbonate
10min is impregnated in liquid, it is dry at 60 DEG C after filtering；It is then added in the aqueous solution containing 10.4g phosphotungstic acid, at 70 DEG C
Stirring to solution is evaporated；By obtained solid in 110 DEG C of dry 8.0 h, then in 400 DEG C of 3.0 h of roasting, catalyst is made,
Its mainly form include: NiO content be 5.0wt%, (NH4)0.7H2.3PW12O40Content is 10wt%, Al2O3Content is 75.0wt%,
SiO2Content is 9.0 wt%.
(3) catalyst characterization:
It is taken a little in the surrounding in catalyst granules section and centre, elemental analysis is carried out to each point by SEM, the results showed that
Heteropoly acid ammonium salt content at surrounding each point is substantially suitable, and ammonium heteropoly acids are not detected in intermediate each point, illustrates using this side
The catalyst of method preparation, the dispersion that ammonium heteropoly acids have had on catalyst surface, and be not impregnated with into duct.
(4) evaluation of catalyst:
Evaluating catalyst carries out in atmospheric fixed bed tubular reactor, and raw material is 15wt% ethanol water, mass space velocity
5h-1, 340 DEG C of reaction temperature.Before reaction, catalyst is in N2In 400 DEG C of 2 h of activation under protection, then it is down to reaction temperature and opens
After beginning reaction 4 hours, product is analyzed by gas-chromatography, is calculated ethanol conversion and ethylene selectivity, be the results are shown in Table 1.
Embodiment 2
(1) preparation of catalyst precarsor A, steps are as follows:
The useless Hydrobon catalyst for selecting fixed bed residual hydrogenation commercial plant extracts 40h using petroleum ether solvent,
Dry 8h, roasts 3h at 600 DEG C at 110 DEG C, and pretreated dead catalyst is made (containing MoO3: 11.0 wt%, NiO:
5.7 wt%, V2O5: 3.0 wt%, Al2O3: 69.0 wt%, SiO2: 10.3 wt%).Catalyst is ground to 200 mesh and (refers to by 200
Mesh), 200 grams of powder weight are weighed, 400 mL of ammonium hydroxide that concentration is 25 wt% is added, 6 h, mistake are impregnated in stirring at 60 DEG C
Filter obtains filtrate A and solid insoluble B, by solid insoluble B in 110 DEG C of dry 8h, then weighs 100 grams of powder weight, adds
Enter 850 DEG C roasting after 40 grams of aluminium oxide, be added 1.0mol/L nitric acid solution 45mL, after mixing on banded extruder extrusion at
In 110 DEG C of dry 8h, then in 400 DEG C of roasting 3h, catalyst precarsor A is made in type.
(2) preparation of catalyst, steps are as follows:
85g catalyst precarsor A is added in autoclave, 450 DEG C are warming up under hydrogen atmosphere, at 0.3MPa
4h is handled, reaction temperature is down to, the sorbitol solution that 400g mass concentration is 20% is added, then adjusting Hydrogen Vapor Pressure to 3MPa,
3h is reacted at 260 DEG C, after reaction, catalyst filtration is come out, and is dried at room temperature to carrier surface without liquid phase；Then plus
Enter into the aqueous solution containing 45.2g citric acid, stirring to solution is evaporated at 40 DEG C；It is molten that obtained material is added to ammonium carbonate
10min is impregnated in liquid, it is dry at 60 DEG C after filtering；It is then added in the aqueous solution containing 15.6g phosphotungstic acid, at 70 DEG C
Stirring to solution is evaporated；By obtained solid in 110 DEG C of dry 8.0 h, then in 470 DEG C of 3.0 h of roasting, catalyst is made,
Its mainly form include: NiO content be 4.0wt%, (NH4)0.5H2.5PW12O40Content is 15wt%, Al2O3Content is 73.0wt%,
SiO2Content is 7.3 wt%.
(3) evaluation of catalyst:
Evaluating catalyst carries out in atmospheric fixed bed tubular reactor, and raw material is 15wt% ethanol water, mass space velocity
6h-1, 330 DEG C of reaction temperature.Before reaction, catalyst is in N2In 400 DEG C of 2 h of activation under protection, then it is down to reaction temperature and opens
After beginning reaction 4 hours, product is analyzed by gas-chromatography, is calculated ethanol conversion and ethylene selectivity, be the results are shown in Table 1.
Embodiment 3
(1) preparation of catalyst precarsor A, steps are as follows:
The useless Hydrobon catalyst for selecting fixed bed residual hydrogenation commercial plant extracts 40h using petroleum ether solvent,
Dry 8h, roasts 3h at 600 DEG C at 110 DEG C, and pretreated dead catalyst is made (containing MoO3: 11.0 wt%, NiO:
5.7 wt%, V2O5: 3.0 wt%, Al2O3: 69.0 wt%, SiO2: 10.3 wt%).Catalyst is ground to 200 mesh and (refers to by 200
Mesh), 200 grams of powder weight are weighed, 400 mL of ammonium hydroxide that concentration is 25 wt% is added, 6 h, mistake are impregnated in stirring at 60 DEG C
Filter obtains filtrate A and solid insoluble B, by solid insoluble B in 110 DEG C of dry 8h, then weighs 100 grams of powder weight, adds
Enter after 850 DEG C of roastings 8 grams of aluminium oxide, is added 1.0mol/L nitric acid solution 40mL, the extruded moulding on banded extruder after mixing,
In 110 DEG C of dry 8h, then in 400 DEG C of roasting 3h, catalyst precarsor A is made.
(2) preparation of catalyst, steps are as follows:
90g catalyst precarsor A is added in autoclave, 450 DEG C are warming up under hydrogen atmosphere, at 0.3MPa
4h is handled, reaction temperature is down to, the sorbitol solution that 400g mass concentration is 20% is added, then adjusting Hydrogen Vapor Pressure to 3MPa,
3h is reacted at 260 DEG C, after reaction, catalyst filtration is come out, and is dried at room temperature to carrier surface without liquid phase；Then plus
Enter into the aqueous solution containing 45.0g citric acid, stirring to solution is evaporated at 40 DEG C；It is molten that obtained material is added to ammonium carbonate
10min is impregnated in liquid, it is dry at 60 DEG C after filtering；It is then added in the aqueous solution containing 18.7g phosphotungstic acid, at 70 DEG C
Stirring to solution is evaporated；By obtained solid in 110 DEG C of dry 8.0 h, then in 470 DEG C of 3.0 h of roasting, catalyst is made,
Its mainly form include: NiO content be 5.0wt%, (NH4)0.5H2.5PW12O40Content is 18wt%, Al2O3Content is 67.0wt%,
SiO2Content is 9.1 wt%.
(3) evaluation of catalyst:
Evaluating catalyst carries out in atmospheric fixed bed tubular reactor, and raw material is 15wt% ethanol water, mass space velocity
7h-1, 330 DEG C of reaction temperature.Before reaction, catalyst is in N2In 400 DEG C of 2 h of activation under protection, then it is down to reaction temperature and opens
After beginning reaction 4 hours, product is analyzed by gas-chromatography, is calculated ethanol conversion and ethylene selectivity, be the results are shown in Table 1.
Comparative example 1
In embodiment 3,85g catalyst precarsor A is added in C6 alkane solvent, impregnates 10min, then filters, room
The lower drying of temperature is to carrier surface without liquid phase；It is then added in the aqueous solution containing 58.0g citric acid, stirs at 40 DEG C to molten
Liquid is evaporated；Obtained material, which is added in sal volatile, impregnates 10min, dry at 40 DEG C after filtering；It is then added to and contains
In the aqueous solution for having 18.7g phosphotungstic acid, stirring to solution is evaporated at 40 DEG C；By obtained solid in 110 DEG C of dry 8.0 h,
Then in 470 DEG C of 3.0 h of roasting, catalyst is made, wherein NiO content is 5.0wt%, (NH4)0.5H2.5PW12O40Content is
18wt%, Al2O3Content is 67.0wt%, SiO2Content is 9.1 wt%.
The evaluation of catalyst the results are shown in Table 1 with embodiment 3, ethanol conversion and ethylene selectivity.
The conversion ratio and selectivity of 1 each catalyst of table
| Embodiment | Conversion ratio, wt% | Selectivity, wt% |
| Embodiment 1 | 98.9 | 98.7 |
| Embodiment 2 | 99.1 | 98.6 |
| Embodiment 3 | 99.0 | 98.8 |
| Comparative example 1 | 97.8 | 96.3 |
By 1 result of table as it can be seen that the activity of the catalyst of the method for the present invention preparation, selectivity are significantly better than comparative example.
Claims (20)
1. a kind of utilization method of useless hydrogenation catalyst, comprising:
(1) pretreated useless hydrogenation catalyst is ground；
(2) dead catalyst powder will be obtained in step (1) and be added in ammonium hydroxide to impregnate, then filter, obtain solid insoluble；
(3) after drying by the solid insoluble in step (2), aluminium oxide, binder, acid solution kneading and compacting is added, through dry
Dry and roasting, obtains catalyst precarsor A；
(4) the resulting catalyst precarsor A of step (3) is added in autoclave, reduction treatment is carried out to it using hydrogen；
(5) polyalcohol and/or furfuryl aldehyde solution are driven into autoclave, then adjust Hydrogen Vapor Pressure to 2 MPa ~ 4MPa, 100
DEG C ~ 300 DEG C at react 0.5h ~ 5.0h；
(6) after filtering by the material after reaction in step (5), it is dried at room temperature, until sample surfaces without liquid phase, obtain
To catalyst precarsor B；
(7) the catalyst precarsor B that step (6) obtains is added in aqueous solutions of organic acids, heating stirring to solution is evaporated, and is obtained
Catalyst precarsor C；
(8) the catalyst precarsor C that step (7) obtains is added in the alkaline solution containing ammonium, through filtering, at 40 DEG C ~ 90 DEG C
It is dry；Or the catalyst precarsor C that step (7) obtains is adsorbed into ammonia at 40 DEG C ~ 90 DEG C, obtain catalyst precarsor D；
(9) aqueous solution of heteropoly acid is added in the catalyst precarsor D that step (8) obtains, heating stirring to solution is evaporated, warp
To get catalyst for ethanol delydration to ethylene after dry and roasting；
In step (5), the polyalcohol is one of C5~C10 polyalcohol or a variety of；The addition of polyalcohol and/or furfural
The mass ratio of amount and catalyst precarsor A are 2:1 ~ 10:1；In step (7), the organic acid is citric acid, tartaric acid, malic acid
One of or it is a variety of, the organic acid accounts for the 10% ~ 70% of catalyst precarsor A weight.
2. according to the method for claim 1, it is characterised in that: the useless hydrogenation catalyst is that waste residue oil hydrotreating is urged
Agent, alumina-based supports, wherein containing active metal Ni, in 1wt% or more in terms of oxide.
3. according to the method for claim 2, it is characterised in that: in the useless catalyst carrier for hydrgenating, containing silicon, to carry
On the basis of the weight of body, silica content is 8% ~ 18%.
4. according to the method for claim 1, it is characterised in that: in step (1), the pretreatment for the hydrogenation catalyst that gives up is using molten
Agent extracting, then through dry and roasting, dry and roasting condition is as follows: dry 5h ~ 12h at 80 DEG C ~ 120 DEG C, 400 DEG C ~
2h ~ 6h is roasted at 700 DEG C.
5. according to the method for claim 1, it is characterised in that: the hydrogenation catalyst that gives up in step (1) is ground to 200 mesh
More than.
6. method according to claim 1 or 2, it is characterised in that: the concentration of ammonia spirit described in step (2) is
20wt%~40wt%, soaking process need to stir and heat, and the h of soaking time 2h ~ 8, temperature is at 40 DEG C ~ 80 DEG C.
7. method according to claim 1 or 2, it is characterised in that: in step (3), the dry condition of solid insoluble is such as
Under: in 90 DEG C ~ 120 DEG C drying 3 h ~ 12 h；In step (3), after molding, dry and roasting condition is as follows: 90 DEG C ~ 120
DEG C dry h of 3 h ~ 12, then in 300 DEG C ~ 600 DEG C roasting 2 h ~ 6 h.
8. method according to claim 1 or 2, it is characterised in that: in step (3), the additional amount of the aluminium oxide accounts for dry
5wt%~40wt% of dry solid insoluble weight.
9. according to the method for claim 1, it is characterised in that: in step (3), acid solution is dilute acid soln, and acid is selected from salt
The one or more of acid, sulfuric acid, nitric acid, citric acid, acetic acid, phosphoric acid, boric acid；The concentration of acid solution is 0.2 ~ 5.0 mol/L, is added
The acid solution entered is 3wt% ~ 15wt% of drying solid insoluble matter weight.
10. according to the method for claim 1, it is characterised in that: in step (4), the reduction treatment process is as follows: hydrogen
Catalyst precarsor is warming up to 300 DEG C~600 DEG C under gas atmosphere, after handling 4h~8h at 0.1MPa~0.5MPa, is down to anti-
Answer temperature.
11. according to the method for claim 1, it is characterised in that: in step (5), the quality of polyalcohol and/or furfuryl aldehyde solution
Concentration is 5%~35%, and the mass ratio of the additional amount and catalyst precarsor A of polyalcohol and/or furfural is 3:1 ~ 10:1.
12. method according to claim 1 or 2, it is characterised in that: in step (8), catalyst that step (7) is obtained
Precursor C, which is added in the alkaline solution containing ammonium, to be impregnated, and dip time is the min of 5 min ~ 30, is urged what step (7) obtained
Agent precursor C adsorbs ammonia, and adsorption time is the min of 5 min ~ 30, and in step (8), the alkaline solution containing ammonium is ammonia
One of water, sal volatile, ammonium bicarbonate soln are a variety of.
13. method according to claim 1 or 2, it is characterised in that: in step (9), the heteropoly acid be phosphotungstic acid,
One of silico-tungstic acid, phosphomolybdic acid are a variety of.
14. method according to claim 1 or 2, it is characterised in that: drying described in step (9) and roasting condition are as follows:
In 90 DEG C ~ 120 DEG C drying h of 3 h ~ 12, then in 300 DEG C ~ 550 DEG C roasting 2 h ~ 6 h.
15. method according to claim 1 or 2, it is characterised in that: the resulting producing ethylene from dehydration of ethanol catalysis of step (9)
In agent, the content of ammonium heteropoly acids is 5wt% ~ 25wt%；Wherein ammonium heteropoly acids are shown in formula (1)；
Hm(NH4)nYX12O40(1)
Wherein X represents W or Mo, and Y represents Si or P；When Y represents Si, m+n=4, n value is 0.1 ~ 1.0；When Y represents P, m
+ n=3, n value are 0.1 ~ 1.0.
16. according to the method for claim 15, it is characterised in that: step (9) resulting catalyst for ethanol delydration to ethylene
In, the content of ammonium heteropoly acids is 8wt% ~ 20wt%.
17. according to the method for claim 16, it is characterised in that: step (9) resulting catalyst for ethanol delydration to ethylene
In, ammonium heteropoly acids are distributed in the outer surface of dead catalyst.
18. according to the method for claim 1, it is characterised in that: before nickel supplement is loaded to step (3) resulting catalyst
On body A.
19. according to the method for claim 15, it is characterised in that: step (9) resulting catalyst for ethanol delydration to ethylene
In, NiO content is 3wt% ~ 6wt%.
20. according to the method for claim 18, it is characterised in that: step (9) resulting catalyst for ethanol delydration to ethylene
In, NiO content is 3wt% ~ 6wt%.
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| CN111821994B (en) * | 2019-04-18 | 2022-06-07 | 中国石油化工股份有限公司 | Preparation method of demetallization catalyst |
| CN112007625B (en) * | 2019-05-28 | 2023-05-30 | 中国石油化工股份有限公司 | Alpha-alumina carrier, preparation method, silver catalyst and application |
| CN112439399B (en) * | 2019-08-29 | 2023-05-09 | 中国石油化工股份有限公司 | Alpha-alumina carrier, preparation method, silver catalyst and application |
| CN115532322A (en) * | 2022-10-26 | 2022-12-30 | 陕西延长石油（集团）有限责任公司 | Method for improving activity of molecular sieve-containing waste catalyst |
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| CN102441443A (en) * | 2010-10-13 | 2012-05-09 | 中国石油化工股份有限公司 | Method for preparing hydrogenation catalyst from waste catalyst mixture |
| CN102441440A (en) * | 2010-10-13 | 2012-05-09 | 中国石油化工股份有限公司 | Method for preparing hydrogenation catalyst from waste catalyst |
| CN103769173A (en) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | Method for utilizing waste hydro-treatment catalyst |
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| CN101797509A (en) * | 2010-03-26 | 2010-08-11 | 抚顺新瑞催化剂有限公司 | Used lubricating oil complete hydrogenation type regenerated catalyst and preparation method and application thereof |
| CN102441443A (en) * | 2010-10-13 | 2012-05-09 | 中国石油化工股份有限公司 | Method for preparing hydrogenation catalyst from waste catalyst mixture |
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