CN106944137A - The Application way of useless hydrogenation catalyst - Google Patents

The Application way of useless hydrogenation catalyst Download PDF

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CN106944137A
CN106944137A CN201610003157.9A CN201610003157A CN106944137A CN 106944137 A CN106944137 A CN 106944137A CN 201610003157 A CN201610003157 A CN 201610003157A CN 106944137 A CN106944137 A CN 106944137A
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catalyst
acid
catalyst precarsor
added
drying
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CN106944137B (en
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金浩
孙素华
朱慧红
杨光
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China Petroleum and Chemical Corp
Sinopec Fushun Research Institute of Petroleum and Petrochemicals
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China Petroleum and Chemical Corp
Sinopec Fushun Research Institute of Petroleum and Petrochemicals
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
    • C07C1/24—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms by elimination of water
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • C07C2527/14—Phosphorus; Compounds thereof
    • C07C2527/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • C07C2527/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
    • 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

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Catalysts (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention discloses a kind of Application way of useless hydrogenation catalyst.This method includes：After useless hydrogenation catalyst is ground, soaked using ammoniacal liquor, aluminum oxide, binding agent and acid solution are then added in remaining solid carries out kneading and compacting；Then in autoclave, reduction treatment is carried out to it using hydrogen；Polyalcohol and/or furfuryl aldehyde solution are added in autoclave, hydrogenation reaction is carried out；Reacted dry materials are until surface is without liquid phase, then after contact successively with organic acid, ammonium or ammonia, carried heteropoly acid, obtained catalyst for ethanol delydration to ethylene.This method not only make use of hydrogenation active metals component and carrier component in useless hydrogenation catalyst, 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 the catalyst for ethanol delydration to ethylene of gained.

Description

The Application way of useless hydrogenation catalyst
Technical field
The present invention relates to a kind of Application way of useless hydrogenation catalyst, the method that catalyst for ethanol delydration to ethylene is particularly prepared by waste residue oil hydrogenating treatment catalyst.
Background technology
The annual whole world will produce the substantial amounts of dead catalyst that can not be regenerated, and wherein hydrogenation catalyst occupies sizable proportion.Catalyst for hydrotreatment of residual oil service life is short, and can not be regenerated after being inactivated due to the deposition of the impurity such as a large amount of W metals and V, especially in waste residue oil Hydrobon catalyst, it is the metal values oxides such as 20wt%~40wt% molybdenum, cobalt, nickel containing total amount, if these dead catalyst are abandoned or the filler as industries such as buildings, the wasting of resources is not only resulted in, and because the loss of metal causes certain pollution to environment, it is especially more serious to water resource pollution.Recently, discarding of the environmental regulation to dead catalyst is more and more stricter.Useless hydrogenation catalyst is by U.S. environment protection mechanism（USEPA）It is considered danger wastes.
The treatment technology of current dead catalyst mainly includes：1. burn, be 2. milled, 3. oxidizing roasting, 4. alkaline leaching reclaims molybdenum, vanadium, 5. acidic leaching Call Provision, nickel, 6. waste sludge discharge etc..It is a kind of preferably selection to reclaim the metal in dead catalyst, can not only be economized on resources, and can reduce environmental pollution.But some problems of existing dead catalyst metal recovery technology generally existing：Not exclusively, what is had only reclaims one or two therein to the valuable metal recoveries such as vanadium, molybdenum, cobalt, nickel；The rate of recovery is relatively low, and the usual rate of recovery only has the % of 70 %~80.Metal recovery processes are a kind of preferably selection for the catalyst having had no value for use really, but its own benefit is not obvious.Especially in China, because the price of hydrogenation catalyst carried metal is relatively inexpensive, so from useless hydrogenation catalyst extract reclaim metal except environmental benefit preferably in addition to, economic benefit is not obvious.So, from environment and economic viewpoint, using dead catalyst for raw material come to generate other value products be a preferably selection.
Useless hydrogenation catalyst is also commonly used for preparing new hydrogenation catalyst, but typically slop cut oil hydrogenation catalysts.Such as US4888316 is to grind useless Hydrobon catalyst, adds salic material, through the processing procedure such as be molded, make charcoal, obtains the Hydrobon catalyst that can be continuing with.CN1552521A is that a small amount of active metal component and then regeneration are added into useless Hydrobon catalyst powder, obtains new Hydrobon catalyst.Change very little of the above method to Hydrobon catalyst part of giving up, and the catalyst of new same purposes is prepared according to the purposes of dead catalyst, by way of increasing Component Vectors or active metal, the raising of catalyst combination property largely still relies on the performance of original catalyst.Waste residue oil hydrogenating treatment catalyst is due to wherein having deposited substantial amounts of metal impurities, cover catalyst surface, reduce number of active center, or blocking catalyst aperture, the utilization of inner surface is hindered, catalyst is difficult by regenerating activity recovery, that is, being used in and prepare new hydrogenation catalyst, also catalyst performance can be made a big impact, causes its rapid deactivation.
Some require the hydrotreater of high activity and catalysts selective, after its catalyst inactivation（Or by regeneration）The device for being adapted to other relatively low requirements is used.When hydrotreating catalyst is constantly declined so that the hydrotreater of other low requirements can not also be used, still it is contemplated that it is recycled on some non-hydrogenation plants with using its active, selectivity.CN1354039A describes a kind of method for preparing catalyst of the SCR for nitrogen oxide, the catalyst is prepared using the dead catalyst that the hydrodesulfurization of oil plant is discharged, and acts on and be better protected from the catalyst poisoning produced to sulfur oxide with excellent nitrogen oxide selective removal.CN1359751A describes a kind of for removing catalyst of dioxin and preparation method thereof, the catalyst is prepared by regenerating the dead catalyst discharged from oil plant hydro desulfurization, remove dioxin performance with excellent, and due to regenerated dead catalyst its to prepare cost relatively low.USP20050075528A1 describes sulphur, nitrogen, the technique of aromatic hydrocarbons in a kind of use dead catalyst adsorbing and removing oil product, and the technique uses NiMo/Al2O3And CoMo/Al2O3Type hydrodesulfurization dead catalyst oil purification, using preceding without specially treated, without heating when using.
Ethene is prepared as basic Organic Chemicals and the flagship product of petro chemical industry, about 75% chemical products by raw material of ethene.In recent years, ethanol particularly recyclable organism preparing ethylene by dehydrating ethanol is increasingly valued by people, it has green, sustainable, reaction condition gentle and many advantages such as product ethylene purity height, with the part or all of great potential for replacing obtaining ethene from oil.Catalyst for ethanol delydration to ethylene report is a lot, mainly activated alumina, molecular sieve and heteropoly acid etc..
[Chemical Engineering Technology and the exploitation, 2010,5 (39) such as Li Benxiang：7-9] article that entitled MCM-41 loads Catalyzed by Silicotungstic Acid producing ethylene from dehydration of ethanol is reported, catalyst is prepared using infusion process.CN200910057539.X discloses a kind of catalyst of producing ethylene from dehydration of ethanol.The catalyst is using aluminum oxide as carrier, and active component is heteropoly acid, is prepared using kneading method.Above-mentioned catalyst shows higher catalytic activity and selectivity when using high concentration ethanol as raw material, but when using low-concentration ethanol as raw material, catalyst activity is decreased obviously, and stability is bad.
The content of the invention
In order to overcome weak point of the prior art, the invention provides a kind of Application way of useless hydrogenation catalyst.This method prepares catalyst for ethanol delydration to ethylene using useless hydrogenation catalyst.This method not only make use of hydrogenation active metals component and carrier component in useless hydrogenation catalyst, and take full advantage of the hydrogenation activity of useless hydrogenation catalyst, solve the pollution problem of dead catalyst, and economize on resources, increase the benefit, technically easily implement, the function admirable of the catalyst for ethanol delydration to ethylene of gained.
The Application way of described useless hydrogenation catalyst, that is, the method that the hydrogenation catalyst that gives up prepares catalyst for ethanol delydration to ethylene, including：
（1）Pretreated useless hydrogenation catalyst is ground；
（2）By step（1）In obtain dead catalyst powder be added in ammoniacal liquor soak, then filter, obtain solid insoluble；
（3）By step（2）In solid insoluble after drying, add aluminum oxide, binding agent, acid solution kneading and compacting, through dry and be calcined, obtain catalyst precarsor A；
（4）By step（3）The catalyst precarsor A of gained is added in autoclave, and reduction treatment is carried out to it using hydrogen；
（5）Polyalcohol and/or furfuryl aldehyde solution are driven into autoclave, Hydrogen Vapor Pressure is then adjusted to 2 MPa ~ 4MPa, 0.5h ~ 5.0h is reacted at 100 DEG C ~ 300 DEG C；
（6）By step（5）In reacted material after filtering, be dried at room temperature, until sample surfaces are without liquid phase, obtain catalyst precarsor B；
（7）By step（6）Obtained catalyst precarsor B is added in aqueous solutions of organic acids, and heating stirring to solution is evaporated, and obtains catalyst precarsor C；
（8）By step（7）Obtained catalyst precarsor C is added in the alkaline solution containing ammonium, through filtering, is dried at 40 DEG C ~ 90 DEG C；Or by step（7）Obtained catalyst precarsor C adsorbs ammonia at 40 DEG C ~ 90 DEG C, obtains catalyst precarsor D；
（9）The aqueous solution of heteropoly acid is added to step（8）In obtained catalyst precarsor D, heating stirring to solution is evaporated, and after drying and roasting, produces catalyst for ethanol delydration to ethylene.
Described useless hydrogenation catalyst can be the discarded hydrogenation catalyst in any source, typically using vib and/or group VIII metal as active metal component, alumina-based supports, do not reach former reaction such as to require, or due to level with reason without the catalyst for hydrotreatment of residual oil that is used in the fixed bed or ebullated bed of complete deactivation, especially residuum hydrodesulfurization catalyst, hydrotransforming catalyst for residual oil etc..The hydrogenation catalyst that wherein gives up preferably comprises active metal Ni, in more than 1wt% in terms of oxide, preferably more than 3wt%.Other active metal components such as Co can also be contained in described dead catalyst, the one or more in adjuvant component, such as titanium, boron, silicon etc., preferably silicon can also be contained.On the basis of the weight of carrier, silica content is 8% ~ 18%.Described waste residue oil hydrogenating treatment catalyst typically has the deposition of the impurity such as part metals Ni and V.
Step（1）In, the pretreatment for the hydrogenation catalyst that gives up can use solvent extraction process, then through drying and being calcined.The solvent typically used can be the one or more in petroleum ether, toluene.Dry and roasting condition is as follows：5h ~ 12h is dried at 80 DEG C ~ 120 DEG C, 2h ~ 6h is calcined at 400 DEG C ~ 700 DEG C.
Step（1）In give up hydrogenation catalyst grind to more than 200 mesh.
Step（2）Described in the concentration of ammonia spirit be generally 20wt%~40wt%, immersion process needs to stir and heated, the h of soak time 2h ~ 8, and temperature is at 40 DEG C ~ 80 DEG C.
Step（2）The main purpose soaked with ammoniacal liquor is to remove the Mo and V in dead catalyst, and retains the Ni on dead catalyst and carrier component such as aluminum oxide etc..
Step（3）In, the condition that solid insoluble is dried is as follows：In 90 DEG C ~ 120 DEG C dryings 3 h~12 h。
Step（3）In, after shaping, dry and the condition of roasting is as follows：In 90 DEG C ~ 120 DEG C dryings 3 The h of h ~ 12, is then calcined the h of 2 h ~ 6 at 300 DEG C ~ 600 DEG C.
Step（3）In, aluminum oxide aluminum oxide used when being conventional carrier preparation and its its precursor, the addition of aluminum oxide account for 5wt%~40wt% of drying solid insoluble matter weight.
Step（3）In, acid solution is dilute acid soln, and acid can be selected from hydrochloric acid, sulfuric acid, nitric acid, citric acid, acetic acid, phosphoric acid, the preferably one or more of boric acid, hydrochloric acid or nitric acid；The concentration of acid solution is generally 0.2 ~ 5.0 mol/L.The acid solution of addition is 3wt% ~ 15wt% of drying solid insoluble matter weight.
Step（4）In, described reduction treatment process is as follows：Catalyst precarsor is warming up to 300 DEG C~600 DEG C under hydrogen atmosphere, is handled under 0.1MPa~0.5MPa after 4h~8h, is down to reaction temperature.Wherein reduction treatment can use pure hydrogen, it would however also be possible to employ the hydrogen containing inert gas, and hydrogen volume concentration is 30% ~ 100%.
Step（5）In, described polyalcohol is the one or more in C5~C10 polyalcohols, the preferably one or more in xylitol, sorbierite, mannitol, arabite；The mass concentration of polyalcohol and/or furfuryl aldehyde solution is 5%~35%, preferably 5%~30%.The addition of polyalcohol and/or furfural is 2 with catalyst precarsor A mass ratio:1~10:1, preferably 3:1~10:1.
Step（7）In, the organic acid is the one or more in citric acid, tartaric acid, malic acid.Described organic acid accounts for the 10%~70% of catalyst precarsor A weight.
Step（8）In, by step（7）Obtained catalyst precarsor B, which is added in the alkaline solution containing ammonium, to be impregnated, and dip time is generally the min of 5 min ~ 30.By step（7）Obtained catalyst precarsor B absorption ammonias, adsorption time is generally the min of 5 min ~ 30.Step（8）In, the alkaline solution containing ammonium is the one or more in ammoniacal liquor, sal volatile, ammonium bicarbonate soln.
Step（8）In, described ammonia can use pure ammonia, it would however also be possible to employ in the gaseous mixture containing ammonia, mixed gas in addition to ammonia, and other is the one or more in inert gas such as nitrogen, argon gas.
Step（9）In, described heteropoly acid is the one or more in phosphotungstic acid, silico-tungstic acid, phosphomolybdic acid.
Step（7）Or step（9）In, described heating stirring is general to be carried out at 40 DEG C ~ 90 DEG C.
Step（9）Described drying and roasting condition is as follows：In 90 DEG C ~ 120 DEG C dryings 3 The h of h ~ 12, is then calcined the h of 2 h ~ 6 at 300 DEG C ~ 550 DEG C.
Step（9）In the catalyst for ethanol delydration to ethylene of gained, the content of ammonium heteropoly acidses is 5% ~ 25%, preferably 8% ~ 20%；Wherein ammonium heteropoly acidses are shown in formula（1）；
Hm(NH4)nYX12O40（1）
Wherein X represents W or Mo, Y represent Si or P；When Y represents Si, m+n=4, n values are 0.1 ~ 1.0；When Y represents P, m+n=3, n values are 0.1 ~ 1.0.
In the catalyst as made from the inventive method, ammonium heteropoly acidses are distributed in the outer surface of dead catalyst.
Step（9）In the catalyst for ethanol delydration to ethylene of gained, preferably NiO contents are 3% ~ 6%.
, can also be as needed in the inventive method, nickel is suitably supplemented, nickel can load to step using conventional carrying method（3）, can also be in step on the catalyst precarsor A of gained（3）Kneading process in add, such as using infusion process, it is necessary to which by drying and being calcined, described drying and roasting condition be as follows after dipping：In 90 DEG C ~ 120 DEG C dryings 3 The h of h ~ 12, is then calcined the h of 2 h ~ 6 at 300 DEG C ~ 550 DEG C.Nickel source is the one or more in nickel nitrate, nickel acetate.
Present invention also offers a kind of method of producing ethylene from dehydration of ethanol, wherein using the catalyst of the present invention.It is ethylene reaction produced that catalyst of the present invention is particularly suitable for use in low-concentration ethanol raw material dehydration.The concentration of described ethanol raw material is 5wt% ~ 30wt%.In the present invention, the reaction condition of producing ethylene from dehydration of ethanol is as follows：The h of mass space velocity 0.5-1~12 h-1, 280 DEG C ~ 400 DEG C of reaction temperature.
The method of the present invention compared with prior art, with advantages below and feature：
1st, physical property of the inventive method to the hydrogenation catalyst that gives up（Than surface, pore volume and aperture）It is relatively low with mechanical property requirements, be particularly suitable for use in recycling and do not reached former reaction and require, or due to level with reason without the catalyst for hydrotreatment of residual oil that is used in the fixed bed or ebullated bed of complete deactivation.
2nd, the present invention soaks dead catalyst by ammonia spirit, Mo and V in useless hydrogenation catalyst is dissolved in solution, the recycling for alloing it to carry out other purposes improves the utilization rate of dead catalyst.
3rd, the inventive method improves the pore structure of catalyst by adding aluminum oxide into useless hydrogenation catalyst powder, while adding acid solution, thus it is possible to vary supported metal it is scattered, and improve the pore structure of catalyst.
4th, the inventive method takes full advantage of the active metal component in useless hydrogenation catalyst, serves not only as the auxiliary agent of catalyst for ethanol delydration to ethylene, and serve hydrogenation in polyalcohol and/or furfural liquid-phase hydrogenatin reaction；The carrier component of dead catalyst is also taken full advantage of simultaneously, is realized the comprehensive utilization of metal and carrier, is improved resource utilization, has saved great amount of cost.
5th, catalytic polyol and/or furfural liquid-phase hydrogenatin in autoclave using useless hydrogenation catalyst, generates liquid alkane, adsorbs on catalyst precarsor A, can effectively block catalyst precarsor A duct, and produce carbon distribution on catalyst precarsor A during the course of the reaction（Can burn off in follow-up roasting process）Catalyst precarsor A acidity can be weakened to a certain extent, reduce the quantity that acidic site adsorbs ammonia, heteropoly acid is set mainly to be reacted with ammonium salt organic acid generation ammonium heteropoly acidses, contribute to ammonium heteropoly acidses dispersed on useless hydrogenation catalyst surface, avoid assembling, and above-mentioned carbon deposit can be removed through follow-up high-temperature roasting, so effectively remain this Component Vectors acidic site.Catalyst prepared by this method not only has the characteristics of low temperature active is high, selectivity is good, carbon accumulation resisting ability is strong, and good stability.
6th, present invention process technology is novel, and reasonable flowsheet structure, method is simple, it is easy to implement operation, and energy consumption is low.
Embodiment
The solution of the present invention and effect are further illustrated below by specific embodiment.In the present invention, wt% is mass fraction.
Embodiment 1
（1）Catalyst precarsor A preparation, step is as follows：
From the useless Hydrobon catalyst of fixed bed residual hydrogenation commercial plant, using petroleum ether solvent, 40h is extracted, 8h is dried at 110 DEG C, 3h is calcined at 600 DEG C, 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（Refer to and pass through 200 mesh sieves）, 200 grams of powder weight is weighed, the mL of ammoniacal liquor 400 that concentration is 25 wt% is added, 6 h of stirring immersion at 60 DEG C, filtrate A and solid insoluble B are filtrated to get, by solid insoluble B in 110 DEG C of dry 8h, 100 grams of powder weight is then weighed, add 850 DEG C of 19 grams of roasting rear oxidation aluminium, add 1.0mol/L salpeter solution 42mL, be well mixed after on banded extruder extruded moulding, in 110 DEG C of dry 8h, then 3h is calcined at 400 DEG C, catalyst precarsor A is made.
（2）The preparation of catalyst, step is as follows：
90g catalyst precarsors A is added in autoclave, 450 DEG C are warming up under hydrogen atmosphere, 4h is handled under 0.3MPa, reaction temperature is down to, the sorbitol solution that 400g mass concentrations are 20% is added, Hydrogen Vapor Pressure is then adjusted to 3MPa, 3h is reacted at 260 DEG C, after reaction terminates, catalyst filtration is come out, dried at room temperature to carrier surface without liquid phase；It is then added in the aqueous solution containing 21.3g citric acids, stirs to solution and be evaporated at 40 DEG C；Obtained material, which is added in sal volatile, impregnates 10min, is dried after filtering at 60 DEG C；It is then added in the aqueous solution containing 10.4g phosphotungstic acids, stirs to solution and be evaporated at 70 DEG C；By obtained solid in 110 DEG C of dry 8.0 h, be then calcined 3.0 h at 400 DEG C, catalyst be made, its mainly constitute including：NiO contents are 5.0wt%, (NH4)0.7H2.3PW12O40Content is 10wt%, Al2O3Content is 75.0wt%, SiO2Content is 9.0 wt%.
（3）Catalyst characterization：
Taken a little in the surrounding in catalyst granules section and centre, elementary analysis is carried out to each point by SEM, as a result shown：Heteropoly acid ammonium salt content at surrounding each point is substantially suitable, and middle each point is not detected by ammonium heteropoly acidses, illustrates the catalyst prepared using the method, it is scattered that ammonium heteropoly acidses have had on catalyst surface, and is not impregnated with into duct.
（4）The evaluation of catalyst：
Evaluating catalyst is carried out in atmospheric fixed bed tubular reactor, and raw material is 15wt% ethanol waters, mass space velocity 5h-1, 340 DEG C of reaction temperature.Before reaction, catalyst is in N22 h are activated in 400 DEG C under protection, reaction temperature is then down to and starts after reacting 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）Catalyst precarsor A preparation, step is as follows：
From the useless Hydrobon catalyst of fixed bed residual hydrogenation commercial plant, using petroleum ether solvent, 40h is extracted, 8h is dried at 110 DEG C, 3h is calcined at 600 DEG C, 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（Refer to and pass through 200 mesh sieves）, 200 grams of powder weight is weighed, the mL of ammoniacal liquor 400 that concentration is 25 wt% is added, 6 h of stirring immersion at 60 DEG C, filtrate A and solid insoluble B are filtrated to get, by solid insoluble B in 110 DEG C of dry 8h, 100 grams of powder weight is then weighed, add 850 DEG C of 40 grams of roasting rear oxidation aluminium, add 1.0mol/L salpeter solution 45mL, be well mixed after on banded extruder extruded moulding, in 110 DEG C of dry 8h, then 3h is calcined at 400 DEG C, catalyst precarsor A is made.
（2）The preparation of catalyst, step is as follows：
85g catalyst precarsors A is added in autoclave, 450 DEG C are warming up under hydrogen atmosphere, 4h is handled under 0.3MPa, reaction temperature is down to, the sorbitol solution that 400g mass concentrations are 20% is added, Hydrogen Vapor Pressure is then adjusted to 3MPa, 3h is reacted at 260 DEG C, after reaction terminates, catalyst filtration is come out, dried at room temperature to carrier surface without liquid phase；It is then added in the aqueous solution containing 45.2g citric acids, stirs to solution and be evaporated at 40 DEG C；Obtained material, which is added in sal volatile, impregnates 10min, is dried after filtering at 60 DEG C；It is then added in the aqueous solution containing 15.6g phosphotungstic acids, stirs to solution and be evaporated at 70 DEG C；By obtained solid in 110 DEG C of dry 8.0 h, be then calcined 3.0 h at 470 DEG C, catalyst be made, its mainly constitute including：NiO contents are 4.0wt%, (NH4)0.5H2.5PW12O40Content is 15wt%, Al2O3Content is 73.0wt%, SiO2Content is 7.3 wt%.
（3）The evaluation of catalyst：
Evaluating catalyst is carried out in atmospheric fixed bed tubular reactor, and raw material is 15wt% ethanol waters, mass space velocity 6h-1, 330 DEG C of reaction temperature.Before reaction, catalyst is in N22 h are activated in 400 DEG C under protection, reaction temperature is then down to and starts after reacting 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）Catalyst precarsor A preparation, step is as follows：
From the useless Hydrobon catalyst of fixed bed residual hydrogenation commercial plant, using petroleum ether solvent, 40h is extracted, 8h is dried at 110 DEG C, 3h is calcined at 600 DEG C, 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（Refer to and pass through 200 mesh sieves）, 200 grams of powder weight is weighed, the mL of ammoniacal liquor 400 that concentration is 25 wt% is added, 6 h of stirring immersion at 60 DEG C, filtrate A and solid insoluble B are filtrated to get, by solid insoluble B in 110 DEG C of dry 8h, 100 grams of powder weight is then weighed, add 850 DEG C of 8 grams of roasting rear oxidation aluminium, add 1.0mol/L salpeter solution 40mL, be well mixed after on banded extruder extruded moulding, in 110 DEG C of dry 8h, then 3h is calcined at 400 DEG C, catalyst precarsor A is made.
（2）The preparation of catalyst, step is as follows：
90g catalyst precarsors A is added in autoclave, 450 DEG C are warming up under hydrogen atmosphere, 4h is handled under 0.3MPa, reaction temperature is down to, the sorbitol solution that 400g mass concentrations are 20% is added, Hydrogen Vapor Pressure is then adjusted to 3MPa, 3h is reacted at 260 DEG C, after reaction terminates, catalyst filtration is come out, dried at room temperature to carrier surface without liquid phase；It is then added in the aqueous solution containing 45.0g citric acids, stirs to solution and be evaporated at 40 DEG C；Obtained material, which is added in sal volatile, impregnates 10min, is dried after filtering at 60 DEG C；It is then added in the aqueous solution containing 18.7g phosphotungstic acids, stirs to solution and be evaporated at 70 DEG C；By obtained solid in 110 DEG C of dry 8.0 h, be then calcined 3.0 h at 470 DEG C, catalyst be made, its mainly constitute including：NiO contents are 5.0wt%, (NH4)0.5H2.5PW12O40Content is 18wt%, Al2O3Content is 67.0wt%, SiO2Content is 9.1 wt%.
（3）The evaluation of catalyst：
Evaluating catalyst is carried out in atmospheric fixed bed tubular reactor, and raw material is 15wt% ethanol waters, mass space velocity 7h-1, 330 DEG C of reaction temperature.Before reaction, catalyst is in N22 h are activated in 400 DEG C under protection, reaction temperature is then down to and starts after reacting 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 precarsors A is added in C6 alkane solvents, impregnates 10min, then filter, dried at room temperature to carrier surface without liquid phase；It is then added in the aqueous solution containing 58.0g citric acids, stirs to solution and be evaporated at 40 DEG C；Obtained material, which is added in sal volatile, impregnates 10min, is dried after filtering at 40 DEG C；It is then added in the aqueous solution containing 18.7g phosphotungstic acids, stirs to solution and be evaporated at 40 DEG C；By obtained solid in 110 DEG C of dry 8.0 h, 3.0 h then are calcined at 470 DEG C, catalyst are made, wherein NiO contents are 5.0wt%, (NH4)0.5H2.5PW12O40Content is 18wt%, Al2O3Content is 67.0wt%, SiO2Content is 9.1 wt%.
The evaluation be the same as Example 3 of catalyst, ethanol conversion and ethylene selectivity the results are shown in Table 1.
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
The activity of the catalyst prepared from the result of table 1, the inventive method, selectivity are significantly better than comparative example.

Claims (19)

1. a kind of Application way of useless hydrogenation catalyst, including：
（1）Pretreated useless hydrogenation catalyst is ground；
（2）By step（1）In obtain dead catalyst powder be added in ammoniacal liquor soak, then filter, obtain solid insoluble；
（3）By step（2）In solid insoluble after drying, add aluminum oxide, binding agent, acid solution kneading and compacting, through dry and be calcined, obtain catalyst precarsor A；
（4）By step（3）The catalyst precarsor A of gained is added in autoclave, and reduction treatment is carried out to it using hydrogen；
（5）Polyalcohol and/or furfuryl aldehyde solution are driven into autoclave, Hydrogen Vapor Pressure is then adjusted to 2 MPa ~ 4MPa, 0.5h ~ 5.0h is reacted at 100 DEG C ~ 300 DEG C；
（6）By step（5）In reacted material after filtering, be dried at room temperature, until sample surfaces are without liquid phase, obtain catalyst precarsor B；
（7）By step（6）Obtained catalyst precarsor B is added in aqueous solutions of organic acids, and heating stirring to solution is evaporated, and obtains catalyst precarsor C；
（8）By step（7）Obtained catalyst precarsor C is added in the alkaline solution containing ammonium, through filtering, is dried at 40 DEG C ~ 90 DEG C；Or by step（7）Obtained catalyst precarsor C adsorbs ammonia at 40 DEG C ~ 90 DEG C, obtains catalyst precarsor D；
（9）The aqueous solution of heteropoly acid is added to step（8）In obtained catalyst precarsor D, heating stirring to solution is evaporated, and after drying and roasting, produces catalyst for ethanol delydration to ethylene.
2. in accordance with the method for claim 1, it is characterised in that：Described useless hydrogenation catalyst is waste residue oil hydrogenating treatment catalyst, alumina-based supports, wherein containing active metal Ni, in more than 1wt% in terms of oxide.
3. in accordance with the method for claim 2, it is characterised in that：In described useless catalyst carrier for hydrgenating, containing silicon, on the basis of the weight of carrier, silica content is 8% ~ 18%.
4. in accordance with the method for claim 1, it is characterised in that：Step（1）In, the pretreatment of useless hydrogenation catalyst uses solvent extraction, then through drying and being calcined, dries and roasting condition is as follows：5h ~ 12h is dried at 80 DEG C ~ 120 DEG C, 2h ~ 6h is calcined at 400 DEG C ~ 700 DEG C.
5. in accordance with the method for claim 1, it is characterised in that：Step（1）In give up hydrogenation catalyst grind to more than 200 mesh.
6. according to the method described in claim 1 or 2, it is characterised in that：Step（2）Described in the concentration of ammonia spirit be 20wt%~40wt%, immersion process needs to stir and heated, the h of soak time 2h ~ 8, and temperature is at 40 DEG C ~ 80 DEG C.
7. according to the method described in claim 1 or 2, it is characterised in that：Step（3）In, the condition that solid insoluble is dried is as follows：In the h of 90 DEG C ~ 120 DEG C 3 h of drying ~ 12；Step（3）In, after shaping, dry and the condition of roasting is as follows：In the h of 90 DEG C ~ 120 DEG C 3 h of drying ~ 12, the h of 2 h ~ 6 is then calcined at 300 DEG C ~ 600 DEG C.
8. according to the method described in claim 1 or 2, it is characterised in that：Step（3）In, the addition of the aluminum oxide accounts for 5wt%~40wt% of drying solid insoluble matter weight.
9. in accordance with the method for claim 1, it is characterised in that：Step（3）In, acid solution is dilute acid soln, and acid is selected from hydrochloric acid, sulfuric acid, nitric acid, citric acid, acetic acid, phosphoric acid, the one or more of boric acid；The concentration of acid solution is 0.2 ~ 5.0 mol/L, and the acid solution of addition is 3wt% ~ 15wt% of drying solid insoluble matter weight.
10. in accordance with the method for claim 1, it is characterised in that：Step（4）In, described reduction treatment process is as follows：Catalyst precarsor is warming up to 300 DEG C~600 DEG C under hydrogen atmosphere, is handled under 0.1MPa~0.5MPa after 4h~8h, is down to reaction temperature.
11. in accordance with the method for claim 1, it is characterised in that：Step（5）In, described polyalcohol is the one or more in C5~C10 polyalcohols；The mass concentration of polyalcohol and/or furfuryl aldehyde solution is 5%~35%, preferably 5%~30%, and the addition of polyalcohol and/or furfural is 2 with catalyst precarsor A mass ratio:1~10:1, preferably 3:1~10:1.
12. according to the method described in claim 1 or 2, it is characterised in that：Step（7）In, the organic acid is the one or more in citric acid, tartaric acid, malic acid, and described organic acid accounts for the 10% ~ 70% of catalyst precarsor A weight.
13. according to the method described in claim 1 or 2, it is characterised in that：Step（8）In, by step（7）Obtained catalyst precarsor B, which is added in the alkaline solution containing ammonium, to be impregnated, and dip time is the min of 5 min ~ 30, by step（7）Obtained catalyst precarsor B absorption ammonias, adsorption time is the min of 5 min ~ 30, step（8）In, the alkaline solution containing ammonium is the one or more in ammoniacal liquor, sal volatile, ammonium bicarbonate soln.
14. according to the method described in claim 1 or 2, it is characterised in that：Step（9）In, described heteropoly acid is the one or more in phosphotungstic acid, silico-tungstic acid, phosphomolybdic acid.
15. according to the method described in claim 1 or 2, it is characterised in that：Step（9）Described drying and roasting condition is as follows：In the h of 90 DEG C ~ 120 DEG C 3 h of drying ~ 12, the h of 2 h ~ 6 is then calcined at 300 DEG C ~ 550 DEG C.
16. according to the method described in claim 1 or 2, it is characterised in that：Step（9）In the catalyst for ethanol delydration to ethylene of gained, the content of ammonium heteropoly acidses is 5% ~ 25%, preferably 8% ~ 20%；Wherein ammonium heteropoly acidses are shown in formula（1）；
Hm(NH4)nYX12O40（1）
Wherein X represents W or Mo, Y represent Si or P；When Y represents Si, m+n=4, n values are 0.1 ~ 1.0；When Y represents P, m+n=3, n values are 0.1 ~ 1.0.
17. in accordance with the method for claim 16, it is characterised in that：Step（9）In the catalyst for ethanol delydration to ethylene of gained, ammonium heteropoly acidses are distributed in the outer surface of dead catalyst.
18. in accordance with the method for claim 1, it is characterised in that：Nickel supplement is loaded into step（3）On the catalyst precarsor A of gained.
19. according to the method described in claim 16 or 18, it is characterised in that：Step（9）In the catalyst for ethanol delydration to ethylene of gained, NiO contents are 3% ~ 6%.
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