CN100594062C - Method for preparing hydrogenation refined catalyst from waste catalyst - Google Patents
Method for preparing hydrogenation refined catalyst from waste catalyst Download PDFInfo
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- CN100594062C CN100594062C CN200610047867A CN200610047867A CN100594062C CN 100594062 C CN100594062 C CN 100594062C CN 200610047867 A CN200610047867 A CN 200610047867A CN 200610047867 A CN200610047867 A CN 200610047867A CN 100594062 C CN100594062 C CN 100594062C
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Abstract
The present invention relates to a method for preparing hydrogenation refining catalyst by using waste catalyst, in particular, it relates to a method for preparing hydrogenation refining catalyst byusing nickel-containing waste hydrogenation refining catalyst. It is characterized by that firstly, it makes the waste catalyst undergo the processes of acid hydrolysis and precipitation, then adoptsconventional process to prepare the hydrogenation refining catalyst by using said waste catalyst.
Description
Technical field
The present invention relates to a kind ofly prepare nickel/aluminium oxide dead catalyst that the method, particularly reactivity worth of Hydrobon catalyst can not meet the demands by dead catalyst and prepare the method for nickel containing hydro-refining catalyst.
Background technology
The annual whole world will produce a large amount of dead catalyst that can't regenerate.According to statistics, about 50～700,000 tons of the annual dead catalyst that produces in the whole world, and wherein Hydrobon catalyst occupies quite great proportion.Enterprise generally abandons these dead catalyst or is used as the filler of industries such as building, but there is very big problem in this: at first because generally contain precious metals oxides such as molybdenum that total amount is about 20wt%～40wt%, tungsten, cobalt, nickel in the Hydrobon catalyst, so processing can cause the wasting of resources; Secondly because the loss meeting of metal causes certain pollution to environment, especially comparatively serious to water resource pollution.Therefore, how to handle dead catalyst is the problem that correlative study department extremely is concerned about always.
At present the treatment technology of dead catalyst mainly comprises: 1. burn, and 2. abrasive dust, 3. oxidizing roasting, 4. alkalescence leaches and reclaims molybdenum, vanadium, and 5. acid the leaching reclaimed cobalt, nickel, 6. waste sludge discharge etc.The metal that reclaims in the dead catalyst is a kind of selection preferably, not only can economize on resources, and can reduce environmental pollution.But existing some problems of dead catalyst metal recovery technology ubiquity: valuable metals such as vanadium, molybdenum, cobalt, nickel reclaim not exclusively, and what have only reclaims wherein one or both; The rate of recovery is lower, and the rate of recovery has only 70%～80% usually.
CN1072730C has introduced a kind of recovery method of cobalt-molybdenum catalyst, and to the useless cobalt-molybdenum catalyst dipping that repeatedly circulates, dipping solution with zinc displacement cobalt wherein, adds nitric acid recovery MoO earlier then with ammonia
3, the filter residue sulfuric acid dissolution after ammonia soaks adds ammonium sulfate and isolates ammonia-alum, to remove most of aluminium; The a small amount of concentrate of gained removes after the impurity such as iron, adds excess ammonia and makes cobalt form complex compound, goes out cobalt with zinc dust precipitation again.Though extracting the recovery metal from useless Hydrobon catalyst, this has certain environmental benefit, the Hydrobon catalyst relatively low for the carried metal price, and its economic benefit is also not obvious.
US4888316 has introduced a kind of processing method of useless Hydrobon catalyst, and the Hydrobon catalyst that will give up grinds, and adds salic material, through moulding, processing procedure such as make charcoal, obtains the catalyst that can continue to use.Add salic material and can improve pore canal structure of catalyst and acidity, but useless Hydrobon catalyst is not partly had the change of essence, the serviceability of catalyst improves limited, and further the scope of using is restricted.
CN1552521A has introduced and has a kind ofly prepared the method for Hydrobon catalyst by dead catalyst, adds a spot of active metal component and regenerate then in useless Hydrobon catalyst powder.Though this method can improve activity of such catalysts to a certain extent, process more complicated, and activity of such catalysts less stable, loss of activity is very fast, and service life is shorter.
Summary of the invention
At the deficiencies in the prior art, the invention provides a kind of method that can effectively utilize useless Hydrobon catalyst, this method can obtain high performance catalyst, and economizes on resources, increases the benefit, and implements easily technically.
The present invention be may further comprise the steps by the method that dead catalyst prepares Hydrobon catalyst:
A, nickeliferous useless hydrogenation catalyst add the strong acid dissolving, filter then and remove solid insoluble, and nickeliferous useless catalyst carrier for hydrgenating is an aluminium oxide;
B, the filtrate pH value that steps A is obtained are adjusted to 5.0～7.2, add alkaline precipitating agent then and precipitate, sediment washing, drying;
C, with the material roasting that step B obtains, moulding promptly obtains final catalyst then; Or first moulding, roasting obtains final catalyst then.
Wherein the nickeliferous dead catalyst described in the steps A comprises all petrochemical catalysts, nickel content (in oxide) is generally more than the 20wt%, as 20wt%～70wt%, can contain other metal component simultaneously in the catalyst, as molybdenum etc., catalyst carrier is an aluminium oxide.
Dead catalyst preferably carries out the high-temperature roasting processing in the steps A before adding the acid dissolving, to remove materials such as carbon elimination and sulphur.Sintering temperature is 400 ℃～700 ℃, and roasting time is 3h～10h, and preferred sintering temperature is 500 ℃～600 ℃, and preferred roasting time is 4h～8h.
Strong acid described in the steps A is inorganic acid, simultaneously can add organic acid, be preferably one or more mixtures of the concentrated sulfuric acid, red fuming nitric acid (RFNA), concentrated hydrochloric acid, preferably select the mixed acid of red fuming nitric acid (RFNA) and concentrated hydrochloric acid for use, dead catalyst and strong acid volume ratio are 1: 0.1～1: 15, are preferably 1: 1～1: 10.The concentration of concentrated acid is generally 30wt%～100wt%, and wherein the concentration of the concentrated sulfuric acid is more than 90wt%, and the concentration of concentrated hydrochloric acid is more than 30wt%, and the concentration of red fuming nitric acid (RFNA) is more than 50wt%, and concentrated acid can be directly from the commercial goods.
The solution temperature of the dead catalyst described in the steps A is preferably 30 ℃～70 ℃ at 10 ℃～80 ℃.Course of dissolution is preferably under the stirring condition and carries out.
Before adding precipitating reagent, want regulator solution pH value 5.0～7.2 in the filtrate described in the step B, best pH value 5.5～6.5, used alkaline solution is preferably the solubility alkali hydroxide, as NaOH, ammoniacal liquor (ammonium hydroxide) etc.The precipitation of hydroxide that produced part aluminium this moment.
Alkaline precipitating agent described in the step B is preferably solution such as carbonate, bicarbonate, and as sodium carbonate liquor, solution of potassium carbonate, sodium bicarbonate solution, potassium bicarbonate solution etc., weight concentration is 10%～60%, is preferably 20%～50%.Coprecipitation mode can adopt variety of way, as the filtrate of regulating after the pH value can being joined in the precipitant solution, also precipitant solution can be joined in the filtrate of regulating pH value or two kinds of solution mix (and flowing mixing) simultaneously.Be preferably with and flow hybrid mode precipitation, stir while dripping, the pH value of mixed solution should be in 8.0～10 scopes, precipitation process control temperature is 30～70 ℃, precipitation finishes the back at 30～70 ℃ of down aging 2h～10h, mixture is through filtering, till solids spends deionised water sodium ion (or potassium ion) to the filtrate and conforms to quality requirements.
The baking temperature that filters the gained filter cake among the step B is 80 ℃～130 ℃, and the time is 3h～10h, and preferred baking temperature is 100 ℃～120 ℃, and be 4h～8h preferred drying time.
Sintering temperature described in step B or the step C is 400 ℃～700 ℃, is preferably 500 ℃～600 ℃, and roasting time is 3h～10h hour, is preferably 4～8 hours.
In the step C forming process, generally need to add an amount of peptizing agent, the peptizing agent addition accounts for 0.5%～3.5% of dead catalyst weight, is preferably 1.5%～3.0%.Peptizing agent is this area peptizing agent commonly used, as salpeter solution etc.
Method of the present invention compared with prior art has the following advantages and characteristics:
1) flow process of the present invention is simple, adopts make catalyst one step of method of co-precipitation, avoided conventional old metal reclaim in loaded down with trivial details step such as metal separation, investment and operating cost are greatly reduced.
2) technology novelty of the present invention, reasonable flowsheet structure can realize the comprehensive recovery of metal and carrier, improves the utilization rate of resource.
3) the inventive method can make metal change free state into by add acid solution in useless Hydrobon catalyst, adds aqueous slkali, again moulding under optimum conditions, metal is redistributed, helped the raising of catalyst activity, prolong the service life of catalyst.
4) the inventive method is dissolved dead catalyst with strong acid, and the pH value of adjusting solution then is to certain limit, makes aluminium partly precipitated in advance wherein, adds alkaline precipitating agent then, and solution metal is all formed sediment.When this method had avoided conventional coprecipitation to prepare catalyst, reactive metal entered the mutually more deficiency of caltalyst, had improved the utilization rate of reactive metal, had improved the serviceability of catalyst.The inventive method flow process is simple, realizes continued operation easily, improves the recovery and the utilization rate of metallic nickel.
The specific embodiment
Give further instruction below by embodiment to technology of the present invention.
The relative activity of catalyst is estimated on anti-little in following examples.Main operating condition is catalyst amount: 10ml; Feedstock oil: 2000 μ g/g thiophene/hexadecanes; Volume space velocity: 2.0h
-1Reaction pressure: 4.0MPa; Hydrogen to oil volume ratio: 500.
Embodiment 1
Ni/Al will give up
2O
3(contain 40.9wt%NiO, 1.58wt%C, 5.02wt%S, 0.12wt%Fe, all the other are Al to Hydrobon catalyst
2O
3) 100g handles through 550 ℃ of constant temperature 4 hours, be crushed to particle and surpass 95% less than 120 orders; Add the 1000ml concentrated sulfuric acid (weight concentration is 98%) then, constant temperature stirs under 30 ℃ of conditions, up to solid complete soln almost, approximately needs 4h, filters and collects filtrate, adds ammoniacal liquor and regulates filtrate PH to 6.0, drips weight concentration and be 30% Na in filtrate
2CO
3Solution, control precipitation process pH value is about 9.0, the precipitation process temperature is controlled to be about 50 ℃, complete post precipitation is aging 4h under 50 ℃,, after filtration, and with 3000ml deionized water washing three times, filter cake is through 110 ℃ of dry 4h, obtain solid 83 grams, add 3 gram red fuming nitric acid (RFNA) and suitable quantity of water, extruded moulding is a 1.0mm cylinder bar, behind 550 ℃ of roasting 3h, be catalyst of the present invention, it is numbered C-1, and physico-chemical property and activity rating the results are shown in Table 1.
Embodiment 2
The useless Ni/Al that uses among the embodiment 1
2O
3Catalyst 100g handled through 580 ℃ of constant temperature in 3.5 hours, was crushed to particle and surpassed 95% less than 70 orders; Add the 900ml concentrated sulfuric acid (weight concentration is 98%) and concentrated hydrochloric acid (weight concentration is 33%) mixed solution then, volume ratio is 1: 1, constant temperature stirs under 40 ℃ of conditions, up to solid complete soln almost, approximately need 4.5h, filter and collect filtrate, add ammoniacal liquor and regulate filtrate PH maintenance 5.5, the dropping weight concentration is 35% Na in filtrate
2CO
3Solution keeps pH value 8, and temperature is 40 ℃, post precipitation is at 40 ℃ of down aging 5h, after filtration, and with 3000ml deionized water washing three times, filter cake is behind 110 ℃ of dry 4h, compression molding, behind 550 ℃ of roasting 5h, obtain solid 85 grams again, be catalyst of the present invention, it is numbered C-2, and physico-chemical property and activity rating the results are shown in Table 1.
Embodiment 3
With the useless Ni/Al that uses among the embodiment 1
2O
3Hydrobon catalyst 100g handled through 550 ℃ of constant temperature in 4 hours, was crushed to particle and surpassed 95% less than 250 orders; Add 900ml concentrated hydrochloric acid (weight concentration is 35%) and red fuming nitric acid (RFNA) (weight concentration is 65%) mixed solution then, volume ratio is 3: 1, constant temperature stirs under 50 ℃ of conditions, up to solid complete soln almost, approximately need 3.5h, filter and collect filtrate, add ammoniacal liquor and regulate filtrate PH maintenance 6.5, the dropping weight concentration is 35% Na in filtrate
2CO
3Solution, to pH value 10, temperature is 60 ℃, post precipitation is at 60 ℃ of down aging 5h,, after filtration, and with 3000ml deionized water washing three times, filter cake is behind 110 ℃ of dry 4h and 550 ℃ of roasting 5h, obtain solid 88 grams, compression molding is catalyst of the present invention, it is numbered C-3, and physico-chemical property and activity rating the results are shown in Table 1.
Embodiment 4
The Ni/Al that will give up that uses among the embodiment 1
2O
3Hydrobon catalyst powder 100g handled through 550 ℃ of constant temperature in 4 hours, was crushed to particle and surpassed 95% less than 250 orders; Add 1200ml sulfuric acid (weight concentration is 98%), concentrated hydrochloric acid (weight concentration is 35%) and red fuming nitric acid (RFNA) (weight concentration is 65%) mixed solution then.Constant temperature stirs under 50 ℃ of conditions, up to solid complete soln almost, approximately needs 5.5h, filters and collects filtrate, and all the other processing methods are catalyst of the present invention with embodiment 1, and it is numbered C-4, and physico-chemical property and activity rating the results are shown in Table 1.
Comparative example 1
According to CN1552521A embodiment 1 disclosed method, both with the useless Ni/Al that uses among the embodiment 1
2O
3The Hydrobon catalyst powder is ground to 250 orders; Sneak into the NiO porphyrize of 2.0w% then, add the binding agent moulding of 20w% again; Then, under the following conditions to this catalyst regenerate (activation); With the catalyst regenerating unit of packing into, with inert nitrogen gas device is replaced earlier, then oxygen content is progressively increased to 2.5v% heats up constant temperature 2h, constant temperature 2h 200 ℃ time the, constant temperature 1.5h 290 ℃ time the, constant temperature 3h 490 ℃ time the in the time of 120 ℃.The gained activating catalyst be numbered C-5, physico-chemical property and activity rating the results are shown in Table 1.
Comparative example 2
The useless Ni/Al that uses in the comparative example 1
2O
3The Hydrobon catalyst powder adds the binding agent moulding of 20w%.Under the condition identical, catalyst is activated then with comparative example 1.The gained catalyst is numbered C-6, and physico-chemical property and activity rating the results are shown in Table 1.
Embodiment 1～4, and the physical and chemical performance of the catalyst that obtains in the Comparative Examples 1～2 and activity rating result all see Table 1.
Table 1 embodiment and comparative example prepare the character and the performance of catalyst
As can be seen from Table 1, if the relative activity with the catalyst that obtains in the comparative example 2 is a benchmark, dead catalyst is molten through acid, after precipitation and the moulding, reactive metal state of aggregation species, pore volume, specific area and intensity do not appear in catalyst surface all to be increased to some extent, especially active increasing significantly.In addition, be the better effects if of 3: 1 mixed solution dissolving dead catalyst with concentrated hydrochloric acid and red fuming nitric acid (RFNA) volume ratio, for nickel containing hydro-refining catalyst, compression molding more helps the raising of catalyst activity.
Claims (8)
1, a kind ofly prepare the method for Hydrobon catalyst by dead catalyst, the present invention be may further comprise the steps by the method that dead catalyst prepares Hydrobon catalyst:
A, nickeliferous useless hydrogenation catalyst is added strong acid dissolving, filter then and remove solid insoluble, nickeliferous useless catalyst carrier for hydrgenating is an aluminium oxide;
B, the filtrate pH value that steps A is obtained are adjusted to 5.0～7.2, add alkaline precipitating agent then and precipitate, sediment washing, drying;
C, with the material roasting that step B obtains, moulding promptly obtains final catalyst then; Or first moulding, roasting obtains final catalyst then;
Wherein the nickeliferous dead catalyst described in the steps A is 20wt%～70wt% in the nickel content of oxide.
2, in accordance with the method for claim 1, it is characterized in that dead catalyst carries out the high-temperature roasting processing in the steps A before adding the acid dissolving, sintering temperature is 400 ℃～700 ℃, and roasting time is 3h～10h.
3, in accordance with the method for claim 1, it is characterized in that the strong acid described in the steps A is inorganic acid, dead catalyst and strong acid volume ratio are 1: 0.1～1: 15.
4, in accordance with the method for claim 1, it is characterized in that the strong acid described in the steps A is one or more mixtures in the concentrated sulfuric acid, red fuming nitric acid (RFNA) and the concentrated hydrochloric acid, dead catalyst and strong acid volume ratio are 1: 1～1: 10.
5, in accordance with the method for claim 1, it is characterized in that the solution temperature of the dead catalyst described in the steps A is at 10 ℃～80 ℃.
6, in accordance with the method for claim 1, it is characterized in that the pH value described in the step B is adjusted to 5.5～6.5, use the pH value of sodium hydroxide solution or ammoniacal liquor regulator solution.
7, in accordance with the method for claim 1, it is characterized in that the alkaline precipitating agent described in the step B is carbonate or bicarbonate solution, solution weight concentration is 10%～60%.
8, in accordance with the method for claim 1, it is characterized in that step B adopts and stream hybrid mode precipitation, the pH value of post precipitation mixed solution is 8.0～10, and precipitation process control temperature is 30～70 ℃, and precipitation finishes the back at 30～70 ℃ of down aging 2h～10h.
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Families Citing this family (10)
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| CN102441440B (en) * | 2010-10-13 | 2014-05-21 | 中国石油化工股份有限公司 | Method for preparing hydrogenation catalyst from waste catalyst |
| CN103769173B (en) * | 2012-10-24 | 2016-02-10 | 中国石油化工股份有限公司 | A kind of Application way of useless hydrotreating catalyst |
| CN103769136B (en) * | 2012-10-24 | 2015-10-21 | 中国石油化工股份有限公司 | A kind of preparation method of oxidative dehydrogenation of propane catalyst |
| CN103230798A (en) * | 2013-04-26 | 2013-08-07 | 沈阳三聚凯特催化剂有限公司 | Hydrogen desulfurization catalyst and preparation method thereof |
| CN103599796B (en) * | 2013-11-06 | 2016-10-05 | 太仓市方亮精细合金厂 | A kind of renovation process of alloyed powder catalyst |
| CN105727972B (en) * | 2014-12-06 | 2018-02-09 | 中国石油化工股份有限公司 | A kind of method for preparing catalyst for synthesizing gas by reforming methane with co 2 |
| CN106916921B (en) * | 2015-12-28 | 2019-06-18 | 正大能源材料(大连)有限公司 | A method of deoxidier is prepared using waste oil fat hydrogenation catalyst |
| CN106513060A (en) * | 2016-10-13 | 2017-03-22 | 中海油天津化工研究设计院有限公司 | Deactivated oil hydrogenation catalyst regeneration method |
| CN106824270B (en) * | 2017-02-21 | 2019-05-28 | 清华大学 | A kind of mixed acid catalyst system and the application in production gasoline alkylate |
| CN110655948A (en) * | 2018-06-30 | 2020-01-07 | 中国石油化工股份有限公司 | Heavy oil hydrotreating method |
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