CN110075866A - A kind of palladium catalyst regeneration method of high activity - Google Patents
A kind of palladium catalyst regeneration method of high activity Download PDFInfo
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- CN110075866A CN110075866A CN201910500638.4A CN201910500638A CN110075866A CN 110075866 A CN110075866 A CN 110075866A CN 201910500638 A CN201910500638 A CN 201910500638A CN 110075866 A CN110075866 A CN 110075866A
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/90—Regeneration or reactivation
- B01J23/96—Regeneration or reactivation of catalysts comprising metals, oxides or hydroxides of the noble metals
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/02—Heat treatment
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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
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
- B01J38/60—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using acids
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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
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
- B01J38/64—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using alkaline material; using salts
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Abstract
The present invention, which provides one kind, can make to handle by existing regeneration method, the palladium catalyst that production requirement is still not achieved in activity reaches the palladium catalyst regeneration method of active or higher active high activity needed for production, comprising the following steps: step 1: the impurity needed in regenerated palladium catalyst is removed；Step 2: the palladium catalyst after removal impurity is reacted with sodium chlorate solution and hydrochloric acid；Step 3: the pH value of the solution after step 2 reaction being adjusted to 4 or more, drying；Step 4: the sample after step 3 drying is roasted.
Description
This case is with the applying date for 2016-09-22, application No. is 201610840632.8, a kind of entitled " palladium catalyst
The divisional application that the patent of invention of regeneration method " carries out for female case.
Technical field
The present invention relates to chemical production technical field more particularly to a kind of palladium catalyst regeneration methods of high activity.
Background technique
Palladium catalyst (Pd-Al in the production of hydrogen peroxide, for anthraquinone hydrogenation2O3), with the extension of use time,
Its activity will gradually decrease, and cannot maintain during normal production when catalyst activity is reduced to, it is necessary to carry out activating and regenerating, with
Restore most of activity, meets normal production requirement.At present there are mainly three types of the regeneration of palladium catalyst: vapor regeneration, aromatic hydrocarbons
Regeneration and oxidation solution regeneration, or by these types of method integrated use.Wherein vapor regeneration is most common method, i.e., to catalysis
It is blown into a large amount of vapor in agent bed, the organic matter of catalyst surface and most inorganic is attached to by hot steam washing
Salt, the activated centre for keeping catalyst surface capped expose again, to restore catalyst activity, this processing method is for urging
Agent top bed regeneration effect is preferable, with deep and catalyst the blocking and cooling of steam, into the steam meeting of bed
Slowly becoming hot water causes flow to strongly reduce, and flows out from lower catalyst bed layer short circuit, leads to lower half major part catalyst
Can not regenerate, whole regeneration effect is bad, and the catalyst service life after regeneration is short, but also that there are working solution wastes is big, at
The disadvantages of this is high.
One kind is disclosed application No. is 201510504199.6 Chinese patent to carry out anthraquinone hydrogen peroxide palladium catalyst
Regeneration method includes the following steps: that 40~60 DEG C of aromatic hydrocarbons impregnate；105~115 DEG C of saturated vapor processing；0~60 DEG C of virtue
Hydrocarbon and trioctyl phosphate solvent soaking；105~115 DEG C of saturated vapor processing.Although the invention restores to a certain extent
The activity of palladium catalyst, but this method regeneration is not thorough enough, not can solve because palladium particle growth causes catalyst activity to reduce
The problem of, cause the activity of regenerated palladium catalyst that the activity of new palladium catalyst is not achieved, meanwhile, cause by repeatedly regenerating
Afterwards, necessary activity needed for production is not achieved in the activity for regenerating palladium catalyst, can only scrap.
Therefore, to by existing regeneration method processing, the catalyst of production requirement is still not achieved in activity, it is necessary to invent one
Kind can make to handle by existing regeneration method, activity needed for the palladium catalyst that production requirement is still not achieved in activity reaches production
Or the palladium catalyst regeneration method of higher active high activity.
Summary of the invention
The technical problems to be solved by the present invention are: providing one kind can make to handle by existing regeneration method, activity is still
The palladium catalyst that production requirement is not achieved reaches the palladium catalyst regeneration side of active or higher active high activity needed for production
Method.
In order to solve the above-mentioned technical problem, the technical solution adopted by the present invention are as follows:
The present invention provides a kind of palladium catalyst regeneration method of high activity, comprising the following steps:
Step 1: the impurity needed in regenerated palladium catalyst is removed；
Step 2: the palladium catalyst after removal impurity is reacted with sodium chlorate solution and hydrochloric acid；
Step 3: the pH value of the solution after step 2 reaction being adjusted to 4 or more, drying；
Step 4: the sample after step 3 drying is roasted.
The beneficial effects of the present invention are: sodium chlorate solution is added on removing the palladium catalyst after impurity and hydrochloric acid carries out
Reaction, this reaction is so that the Metal Palladium of big crystal grain and palladium oxide particle are converted into the palladium chloride of little crystal grain on catalyst, to solve
Certainly because palladium particle growth causes the activity of palladium catalyst to be difficult to the problem of restoring and preferably saves the intensity of aluminium oxide；In palladium
Catalyst added after being reacted with sodium chlorate solution and hydrochloric acid a little alkaline solution adjust palladium catalyst surface acidic-basic property to pH be 4 with
On obtain palladium dydroxide to generate during fixing process palladium compound；Sample after step 3 drying is subjected to high-temperature roasting,
Redistribute palladium catalyst surface, the obtained palladium in regenerated catalyst mainly exists in the form of palladium oxide, the palladium oxide
Field boundary can be showed in situ also with hydrogen with reducing agent prereduction or when catalyst is used in hydrogenation reactor using preceding in catalyst
Original is suitable with the activity of new palladium catalyst using the activity of the regenerated palladium catalyst of the method for the present invention by test discovery.
Specific embodiment
To explain the technical content, the achieved purpose and the effect of the present invention in detail, it is explained below in conjunction with embodiment.
The most critical design of the present invention is: by by big crystal grain Metal Palladium contained on the palladium catalyst of clean drying or
Palladium oxide is dispersed into the palladium chloride of little crystal grain by chemical treatment, to solve in production and application because palladium particle growth causes
The activity of palladium catalyst is difficult to the problem of restoring, and keeps the activity for regenerating palladium catalyst higher than conventional regeneration processes.
The present invention provides a kind of palladium catalyst regeneration method of high activity, comprising the following steps:
Step 1: the impurity needed in regenerated palladium catalyst is removed；
Step 2: the palladium catalyst after removal impurity is reacted with sodium chlorate solution and hydrochloric acid；
Step 3: the pH value of the solution after step 2 reaction being adjusted to 4 or more, drying；
Step 4: the sample after step 3 drying is roasted.
Reaction principle of the invention: utilizing sodium chlorate-hydrochloric acid reaction method, and the big Metal Palladium of crystal grain or palladium oxide particle are turned
The palladium chloride particle of little crystal grain is turned to, to solve conventional regeneration method because the catalyst activity that palladium particle growth is reduced is difficult to
The problem of recovery, treatment process adjust catalyst surface pH value used in alkaline matter be sodium hydroxide potassium hydroxide or
Sodium carbonate potassium carbonate or sodium bicarbonate adjust catalyst surface pH value to 4 or more, catalyst treatment process are generated
The soluble compound of palladium to be converted to palladium dydroxide fixed on a catalyst.
The related reaction of chemical treatment method is as follows:
Main reaction: PdO+2HCl==PdCl2+H2O............(1)
Pd+Cl2=PdCl2.......................(2)
Pd2++2OH?=Pd (OH)2............(3)
The reaction of formula 2 generally carries out in the hydrochloric acid atmosphere of 7%~30% concentration or so.Due to the hydrochloric acid in above-mentioned reaction
There is deep-etching effect to alumina support, will be greatly reduced the intensity of alumina support, in order to mitigate this side effect, the present invention
Active Chlorine is introduced in reaction process, to reduce hydrochloric acid dosage and can mitigate hydrochloric acid to the corrosiveness of alumina support, is added
Strong reaction speed, the preferable intensity for saving aluminium oxide.
The process of Active Chlorine is released in the effect of sodium chlorate and hydrochloric acid:
NaClO3+HCl→HClO3+NaCl......................(4)
NaClO3+3HCl→HClO2+NaCl+Cl2+H2O.............(5)
NaClO2+2HCl→HClO+Cl2+H2O...................(6)
Formula (5), chlorine caused by (6) is more active than the chloride ion that hydrochloric acid is isolated, and can participate in main reaction well.
As can be seen from the above description, the beneficial effects of the present invention are: on removing the palladium catalyst after impurity add chloric acid
Sodium solution and hydrochloric acid are reacted, this reaction is so that the Metal Palladium of big crystal grain and palladium oxide particle are converted into little crystal grain on catalyst
Palladium chloride, to solve the problems, such as that the activity of palladium catalyst is caused to be difficult to restore because of palladium particle growth and can preferably save oxygen
Change the intensity of aluminium；After palladium catalyst is reacted with sodium chlorate solution and hydrochloric acid, addition alkaline solution adjusts palladium catalyst surface acid
Alkalinity to pH be 4 or more, it is therefore an objective to the soluble compound for the palladium that previous reaction generates is converted into palladium dydroxide and is fixed on and is urged
In agent, the operation of benefit palladium and washing operation, palladium dydroxide for being conducive to subsequent catalyst can securely be adsorbed on catalyst surface
On, guarantee the palladium content that catalyst will not be lost in subsequent processing；Sample after step 3 drying is subjected to high-temperature roasting, is obtained
To regenerated oxidized catalyst, which can use with reducing agent or in hydrogenation reactor using preceding
Hydrogen shows field boundary in-situ reducing, activity and new palladium catalyst by test discovery using the regenerated palladium catalyst of the method for the present invention
It is active suitable.
Further, between step 3 and step 4, further include to step 3 drying after sample in, be added palladium chloride and
The mixed liquor of sodium chloride impregnates, filtering, adds water washing until mixed liquor not chloride ion-containing, drying；The water is that temperature is room temperature
To 60 DEG C of pure water.
Seen from the above description, the beneficial effects of the present invention are: palladium chloride and chlorination is added in sample after to step 3 reaction
The miscible aqueous solution of sodium, since palladium chloride water solubility is very low, addition sodium chloride is molten altogether, can form the palladium sodium chloride that can be dissolved in water,
The pH stable of the solution facilitates palladium particle in the reasonable layout of oxidation aluminium surface, and then reasonably supplements palladium in catalyst
Content, further increase regeneration palladium catalyst activity, extend regeneration palladium catalyst service life；Add certain temperature pure water
Washing more thoroughly removes the soluble impurity that catalyst introduces in regenerative process, ensure that the performance of catalyst.
Further, the concrete operations of the step 1 are as follows: 50~70 DEG C of aromatic hydrocarbons of regenerated palladium catalyst will be needed to soak
3~6h is steeped, replaces the primary aromatic hydrocarbons every 0.5h；The palladium catalyst that aromatic hydrocarbons was impregnated drains molten with 30~70 DEG C of alkalinity
Liquid impregnates 4~5h, replaces the primary alkaline solution every 0.5h；The palladium catalyst that alkaline solution was impregnated drains with 30~
90 DEG C of water impregnates, until being soaked with the aqueous solution of palladium catalyst as neutrality.
Seen from the above description, the beneficial effects of the present invention are: by with aromatic hydrocarbons, alkaline solution and water to need it is regenerated
Palladium catalyst is impregnated, and washes away the acidic materials and alkaline matter of remaining organic matter on palladium catalyst, absorption respectively, thus
The regeneration effect of palladium catalyst is avoided to be influenced by the impurity that it is adsorbed；Using with higher temperature aromatic hydrocarbons, alkaline solution and
Water successively to needing regenerated palladium catalyst to impregnate, facilitate organic matter on palladium catalyst, acidic materials, alkaline matter and
Some other impurity shorten soaking time by quick wash, improve regeneration efficiency.
Further, the aromatic hydrocarbons is C9Aromatic hydrocarbons, C10Aromatic hydrocarbons or C9Aromatic hydrocarbons and C10The mixture of aromatic hydrocarbons arbitrary proportion.
Seen from the above description, the beneficial effects of the present invention are: use C9Aromatic hydrocarbons, C10Aromatic hydrocarbons or C9Aromatic hydrocarbons and C10Aromatic hydrocarbons
The mixture of arbitrary proportion carries out first of washing of palladium catalyst, can more effectively remove the substance that palladium catalyst is adhered to
And some organic degradation objects.
Further, the alkaline solution is potassium hydroxide solution, sodium hydroxide solution, ammonium hydroxide, sodium carbonate liquor, carbonic acid
Hydrogen sodium solution, solution of potassium carbonate and potassium bicarbonate solution, the concentration of the alkaline solution are 0.05~0.30mol/L.
Seen from the above description, the beneficial effects of the present invention are: above-mentioned alkaline solution be easier to obtain and cost compared with
It is low, and can achieve the effect of acidic materials on removal palladium catalyst.
Further, it carries out screening out before the step 1 and needs regenerated palladium catalyst, the method for screening are as follows: with 10
Purpose sieve sieves waste and old palladium catalyst, removes partial size in 2mm particle below.
Seen from the above description, the beneficial effects of the present invention are: with sieve removal partial size in 2mm particle below, keep away
Exempt from that particle is too small to cause resistance too big, is not suitable for fixed bed.
Further, the molar ratio of the palladium in the sodium chlorate and palladium catalyst in the sodium chlorate solution is 1: 1~2, institute
The molar ratio for stating the sodium chlorate and hydrochloric acid in sodium chlorate solution is 1: 6~10.
Seen from the above description, the beneficial effects of the present invention are: can guarantee under acid atmosphere most of hydrochloric acid in this way
It reacts with sodium chlorate, while also guaranteeing that the amount of drug used is enough the palladium on catalyst being completely converted into palladium chloride.
Since alumina catalyst support of the hydrochloric acid to palladium catalyst has deep-etching effect, the intensity of alumina support will be greatly reduced, because
This can release the characteristic of Active Chlorine using sodium chlorate and hydrochloric acid effect, be added in the palladium catalyst of washing and drying after removing impurity
Sodium chlorate and hydrochloric acid, so that sodium chlorate is reacted with hydrochloric acid added by major part generates Active Chlorine, Active Chlorine generates palladium chloride with palladium again,
Reduce the amount directly with the hydrochloric acid of catalyst action, slows down hydrochloric acid to the corrosiveness of aluminium oxide, preferably save oxygen
Change the intensity of aluminium, and accelerates reaction speed.
Further, the temperature of the roasting is 500~550 DEG C, and the time of the roasting is 2~4h.
By it is upper description it is found that the beneficial effects of the present invention are: pass through the high-temperature process, palladium chloride can be transformed into
Palladium oxide, and redistribute palladium rationally on the alumina support, the catalyst after being conducive to regeneration has good activity, choosing
Selecting property and service life.
Further, in the step 3 adjust pH value used in alkaline matter be sodium hydroxide, potassium hydroxide, sodium carbonate,
Potassium carbonate or sodium bicarbonate, dosage be need regenerated catalyst dry weight 0.10~0.30%.
Embodiment one
The palladium catalyst regeneration method of the high activity of the present embodiment, includes the following steps:
Pre-processing: sieving waste and old palladium catalyst with the sieve of 10 mesh, removal partial size in 2mm particle below,
It obtains needing regenerated palladium catalyst.
Step 1: weighing 100g needs regenerated palladium catalyst (using the FAH-1Q type fixed bed palladium-oxidation scrapped after 6 years
Al catalysts) in 500mL beaker, the C that 180mL temperature is 60 DEG C is added every time10Aromatic hydrocarbons is impregnated, each foam washing 30min
After isolate aromatic hydrocarbons, add the aromatic hydrocarbons with first time equivalent, so impregnate 9 times, the aromatic hydrocarbons isolated for the last time is in light
Yellow；
Then by the palladium catalyst that above-mentioned aromatic hydrocarbons has impregnated be added every time 160mL concentration be 0.1mol/L, temperature be 30~
50 DEG C sodium hydroxide (NaOH) solution is impregnated, and is removed washing lotion after each foam washing 30min, then add and first time isothermal
The sodium hydroxide solution of isoconcentration, after washing by soaking 10 times, washing lotion is without oil droplet and is in light pink；
Alkaline solution wash after catalyst drain after, then every time with 160mL temperature be 30~50 DEG C deionized water impregnate
It washs, the deionized water with first time isothermal equivalent is added after each foam washing 30min, in the aqueous solution of immersion catalyst is in
Until property.
Step 2: the catalyst after step 1 is cleaned, which is placed in 120 DEG C of drying oven, dries 4h, then at 200 DEG C of drying oven
Dry 4h.The palladium content of palladium catalyst after measuring drying is 0.19%, water absorption rate 86%.After weighing the above-mentioned washing of 30g, drying
Palladium catalyst (in palladium catalyst the molar content of palladium be 30 × 0.0019/106.42=0.000535614 (mol)), be placed in
In 300mL beaker；
1 100mL beaker is taken, the sodium chlorate that 0.0576g purity is 99% is accurately weighed and (takes the molar ratio of sodium chlorate and palladium
It is 1: 1, then sodium chlorate dosage=0.000535614 × 106.44 ÷ 0.99=0.0575866 (g), wherein 106.44 be chloric acid
The molal weight of sodium, 0.99 is the purity of sodium chlorate, it is contemplated that accuracy of balance takes 0.0576g), being dissolved in 26mL temperature is 60 DEG C
Deionized water in, and by this heat sodium chlorate solution pour into the aforementioned 300mL beaker equipped with 30g catalyst, shake beaker,
Make uniform absorption；
It is accurate to measure concentrated hydrochloric acid (concentrated hydrochloric acid dosage=0.000535614 × 7 ÷ 0.012 that 0.31mL concentration is 12mol/L
It is 0.31mL that=0.312 (mL), which is rounded, and wherein 7 times of concentrated hydrochloric acid measurement Metal Palladium mole, the molar concentration of hydrochloric acid are
12mol/L), first with being added in the above-mentioned catalyst for having impregnated sodium chlorate solution after the dilution of 1.0mL deionized water, stirring beaker makes
It contacts with catalyst uniformly, after standing 4h, this sample is placed in baking oven in 120 DEG C of bakings 3h, take out and be placed in one completely
In 300mL beaker.
Step 3: take 1 100mL beaker, accurately weigh 0.06g purity be 96% sodium hydroxide (dosage=30 NaOH ×
0.0019 ÷ 0.96=0.06 (g), taking sodium hydroxide concentration is the 0.19% of catalyst weight, and 0.96 is NaOH purity) it is dissolved in
It in 26mL deionized water, is then added in the 300mL beaker equipped with above-mentioned drying sample, stirs after beaker makes uniform absorption, then
It is placed in baking oven after 120 DEG C of baking 3h, taking-up is placed in a clean 300mL beaker.
Mend palladium: accurately weighing the palladium chloride that 0.0303g purity is 59.5%, (designing regenerated catalyst palladium content is
0.25%, 0.595 is the palladium content of chlorination palladium reagent, palladium chloride additional amount=(0.0025-0.0019) × 30 ÷ 0.595=
0.03025 (g) takes 0.0303g) and 0.04g purity be 96% sodium chloride, be dissolved in 75mL deionized water, this solution be added
In the beaker of sample after above-mentioned drying, after impregnating 1h, filtering removal dipping raffinate.
Washing and drying: it will mend in the solid obtained after palladium, filtering after 100mL deionized water at normal temperature immersion 12h is added, separation
Soak, then with the frequency primary with 100mL deionized water at normal temperature foam washing at interval of 1h, washing to the wash water isolated is with 1%
Silver nitrate solution is examined, and can't check Cl-Until；Catalyst sample after above-mentioned clean is placed in Muffle furnace in 200 DEG C of baking 2h.
Step 4: the sample dried in step 3 is placed in Muffle furnace in 500 DEG C of roasting 4h, namely regenerated palladium catalyst.
The activity of catalyst is evaluated using micro fixed-bed reactor (see " University of Fuzhou's journal (natural science edition) "
4th phase in 2000).50 DEG C of reaction temperature, pressure is normal pressure, mixing speed 1400r/min, and hydrogen source uses H-N ratio for 3:
1 hydrogen nitrogen mixed gas, catalyst loading are 40mL (about 20g), and active testing procatalyst uses hydrogen nitrogen mixed gas in the reactor
In 60~80 DEG C of normal pressure reductase 12 0h in situ.The working solution composition that this experiment uses are as follows: 2- ethyl hydrazine (EAQ) content 130g/L,
Solvent uses the mixture of trioctyl phosphate (TOP) and heavy aromatics, ratio 25/75, and working solution dosage is 240mL.With 1.5h
The H that interior reaction generates2O2Amount as the catalyst hydrogen imitate, for compare different catalysts activity height.
The palladium content analysis of catalyst uses China's oil chemical industry standard SH/T0684-1999 " molecular sieve and oxidation
Palladium content measuring method (atomic absorption spectrography (AAS)) in aluminium-based catalyst " prescriptive procedure progress.
The compression strength of catalyst carries out on DL5 type intelligence detector for strength of particles, each sample take at random 30 into
Row test, takes the average value of 30 particle test values as the test result of the sample.
The test result of the activity of catalyst, palladium content and compression strength is listed in table 1.
Embodiment two
The step of repeating embodiment one, is only changed to 1: 1.5 for the molar ratio of sodium chlorate and palladium in wherein step 2, chloric acid
The molar ratio of sodium and hydrochloric acid is changed to 1: 10, i.e. 1.5 × 106.44 ÷ 0.99=of this example sodium chlorate dosage=0.000535614 ÷
0.0383911 (g), wherein 106.44 be the molal weight of sodium chlorate, 0.99 is the purity of sodium chlorate, it is contemplated that accuracy of balance,
Take 0.0384g) hydrochloric acid dosage be 0.000535614 ÷, 1.5 × 10 ÷ 0.012=0.29756 (mL) rounding be 0.30mL, be used for
The dosage for adjusting the sodium hydroxide of catalyst surface pH value still weighs 0.06g in the ratio of embodiment one, the palladium content of catalyst,
The test method of activity and compression strength is carried out by embodiment one, and data are shown in Table 1.
Embodiment three
The step of repeating embodiment one has only used Na when step 3 adjusts catalyst surface pH value2CO3, sodium carbonate
Hydrolysis ionic equation are as follows:
CO3 2-+H2O==HCO3-+OH-
HCO3 -+H2O ≤=> H2CO3+OH-
It can be seen that the alkali number that the hydrolysis of 1 mole of either sodium carbonate generates is similar to the alkali number of 2 molar sodium hydroxides, sodium carbonate amount is set
For 0.10% (being equivalent to 0.2% that NaOH usage amount is catalyst weight) of catalyst weight, Na thus2CO3Dosage=30 ×
0.001 ÷ 0.995=0.03015 (g) actually weighs 0.0302g, and 0.995 is NaOH purity, remaining is carried out by embodiment one.
The test data of the palladium content of catalyst, activity and compression strength is shown in Table 1.
Example IV
The roasting condition of catalyst in wherein step 4 only is changed to roast at 550 DEG C of temperature by the step of repeating embodiment one
3h is burnt, for the test method of the palladium content of catalyst, activity and compression strength by the progress of embodiment one, data are shown in Table 1.
Embodiment five
This example is regeneration object, weight using the APC-1-Q type fixed bed palladium-aluminium oxide catalyst scrapped after 4 years with factory
The process of multiple embodiment one.The palladium content for measuring the model fresh catalyst is 0.27wt.%, and spent catalyst palladium content is
0.21wt.%.
Pre-processing: sieving waste and old palladium catalyst with the sieve of 10 mesh, removal partial size in 2mm particle below,
It obtains needing regenerated palladium catalyst.
Step 1: weighing 100g needs regenerated palladium catalyst in 500mL beaker, and it is 60 DEG C that 180mL temperature is added every time
C10Aromatic hydrocarbons is impregnated, and is isolated aromatic hydrocarbons after each foam washing 30min, is added the aromatic hydrocarbons with first time equivalent, so impregnates 10
Secondary, the aromatic hydrocarbons isolated for the last time is in light yellow；
Then by the palladium catalyst that above-mentioned aromatic hydrocarbons has impregnated be added every time 160mL concentration be 0.1mol/L, temperature be 30~
50 DEG C sodium hydroxide (NaOH) solution is impregnated, and is removed washing lotion after each foam washing 30min, then add and first time isothermal
The sodium hydroxide solution of isoconcentration, after washing by soaking 10 times, washing lotion is without oil droplet and is in light pink；
Alkaline solution wash after catalyst drain after, then every time with 160mL temperature be 30~50 DEG C deionized water impregnate
It washs, the deionized water with first time isothermal equivalent is added after each foam washing 30min, in the aqueous solution of immersion catalyst is in
Until property.
Step 2: the catalyst after step 1 is cleaned, which is placed in 120 DEG C of drying oven, dries 4h, then at 200 DEG C of drying oven
Dry 4h.The palladium content of palladium catalyst after measuring drying is 0.21%, water absorption rate 82%.After weighing the above-mentioned washing of 30g, drying
Palladium catalyst (in palladium catalyst the molar content of palladium be 30 × 0.0021/106.42=0.000591994 (mol)), be placed in
In 300mL beaker；
Take 1 100mL beaker, accurately weigh 0.0636g purity be 99% sodium chlorate (sodium chlorate dosage=
0.000591994 × 106.44 ÷ 0.99=0.0636483 (g), wherein 106.44 be the molal weight of sodium chlorate, 0.99 is chlorine
The purity of sour sodium, it is contemplated that accuracy of balance takes 0.0636g), it is dissolved in the deionized water that 25mL temperature is 60 DEG C, and this is hot
Sodium chlorate solution pour into the aforementioned 300mL beaker equipped with 30g catalyst, shake beaker, make uniform absorption；
It is accurate to measure concentrated hydrochloric acid (concentrated hydrochloric acid dosage=0.000591994 × 7 ÷ 0.012 that 0.35mL concentration is 12mol/L
It is 0.35mL that=0.345 (mL), which is rounded, and wherein 7 times of concentrated hydrochloric acid measurement Metal Palladium mole, the molar concentration of hydrochloric acid are
12mol/L), first with being added in the above-mentioned catalyst for having impregnated sodium chlorate solution after the dilution of 1.0mL deionized water, stirring beaker makes
It contacts with catalyst uniformly, after standing 4h, this sample is placed in baking oven in 120 DEG C of bakings 3h, take out and be placed in one completely
In 300mL beaker.
Step 3: taking 1 100mL beaker, accurately weigh sodium hydroxide (dosage=30 NaOH that 0.0625g purity is 96%
× 0.002 ÷ 0.96=0.0625 (g), taking sodium hydroxide concentration is the 0.20% of catalyst weight, and 0.96 is NaOH purity) it is molten
It in 25mL deionized water, is then added in the 300mL beaker equipped with above-mentioned drying sample, stirs after beaker makes uniform absorption,
It is placed in baking oven again after 120 DEG C of baking 3h, taking-up is placed in a clean 300mL beaker.
Mend palladium: accurately weighing the palladium chloride that 0.0454g purity is 59.5%, (designing regenerated catalyst palladium content is
0.30%, 0.595 is the palladium content of chlorination palladium reagent, palladium chloride additional amount=(0.003-0.0021) × 30 ÷ 0.595=
0.04538 (g) takes 0.0454g) and 0.05g purity be 96% sodium chloride, be dissolved in 75mL deionized water, this solution be added
In the beaker of sample after above-mentioned drying, after impregnating 1h, filtering removal dipping raffinate.
Washing and drying: it will mend in the solid obtained after palladium, filtering after 100mL deionized water at normal temperature immersion 12h is added, separation
Soak, then with the frequency primary with 100mL deionized water at normal temperature foam washing at interval of 1h, washing to the wash water isolated is with 1%
Silver nitrate solution is examined, and can't check Cl-Until；Catalyst sample after above-mentioned clean is placed in Muffle furnace in 200 DEG C of baking 2h.
Step 4: the sample dried in step 3 is placed in Muffle furnace in 500 DEG C of roasting 4h, namely regenerated palladium catalyst.
Activity, palladium content and the compression strength of catalyst are tested by one method of embodiment, and data are listed in table 1.
Comparative example one
Factory is sieved using FAH-1Q palladium catalyst waste and old after 6 years with the sieve of 10 mesh, removes partial size in 2mm
Then particle below weighs catalyst sample described in 100g in 500mL beaker, it is 60 DEG C that 180mL temperature is added every time
C10Aromatic hydrocarbons is impregnated, and is isolated aromatic hydrocarbons after each foam washing 30min, is added the aromatic hydrocarbons with first time equivalent, so impregnates 9
Secondary, the aromatic hydrocarbons isolated for the last time is in light yellow, is subsequently placed in baking oven after drying 4 hours in 200 DEG C and is down to room temperature
It obtains testing required palladium catalyst.The test method of the activity of catalyst, palladium content and compression strength is carried out by embodiment one,
Data are listed in table 1.
Comparative example two
The process of comparative example one is repeated, only sample is changed to factory and uses APC-1-Q waste and old after 4 years, the work of catalyst
Property, palladium content and compression strength test method carried out by embodiment one, data are listed in table 1.
Comparative example three
Fresh FAH-1Q catalyst is taken, the test method of activity, palladium content and compression strength is carried out by embodiment one,
Data are listed in table 1.
Comparative example four
Take fresh APC-1-Q catalyst, the test method of activity, palladium content and compression strength by embodiment one into
Row, data are listed in table 1.
Evaluation results are shown in Table 1 for catalyst activity.
The activity comparison of several catalyst of table 1.
As seen from Table 1, for spent catalyst after regeneration method of the present invention processing, activity and palladium content basically reach new catalysis
The level of agent, and mechanical strength is suitable with untreated regeneration procatalyst.
In conclusion the palladium catalyst regeneration method of high activity provided by the invention, the palladium catalyst after removing impurity
Upper addition sodium chlorate solution and hydrochloric acid react, this reaction so that on catalyst big crystal grain Metal Palladium particle and palladium oxide grain
Son is converted into the palladium chloride of little crystal grain, thus solve the problems, such as to cause because of palladium particle growth the activity of palladium catalyst be difficult to restore and
Preferably save the intensity of aluminium oxide；A little alkaline solution tune is added after palladium catalyst is reacted with sodium chlorate solution and hydrochloric acid
Save palladium compound of the palladium catalyst surface acidic-basic property to pH for 4 palladium dydroxides derived above to generate during fixing process；It will
Sample after step 3 drying carries out high-temperature roasting, obtains regenerated catalyst palladium oxide, uses the method for the present invention by test discovery
The activity of regenerated palladium catalyst is suitable with the activity of new palladium catalyst；By regenerated to needing with aromatic hydrocarbons, alkaline solution and water
Catalyst is impregnated, washes away the acidic materials and alkaline matter of remaining organic matter on palladium catalyst, absorption respectively, thus
Avoid the activity of regeneration palladium catalyst is influenced by the impurity that it is adsorbed；Palladium chloride and chlorination is added in sample after to step 3 reaction
Sodium solution carries out the content of palladium in supplement palladium catalyst, further increases the activity of regeneration palladium catalyst, extends regeneration palladium chtalyst
The service life of agent；It is washed to the catalyst after palladium is mended to remove the impurity of regenerative process introducing, avoids impurity to urging
The influence of agent activity and selectivity；Sample after overfill palladium, washing is dried and high-temperature roasting, obtains palladium again again
The oxidation state regenerated catalyst of distribution is found by test, using activity and the new palladium of the regenerated palladium catalyst of the method for the present invention
The activity of catalyst is suitable, and compression strength is suitable with the regeneration compression strength of procatalyst.
The above description is only an embodiment of the present invention, is not intended to limit the scope of the invention, all to utilize this hair
Equivalents made by bright description are applied directly or indirectly in relevant technical field, are similarly included in this hair
In bright scope of patent protection.
Claims (7)
1. a kind of palladium catalyst regeneration method of high activity, which comprises the following steps:
Step 1: the impurity needed in regenerated palladium catalyst is removed；
Step 2: by remove impurity after palladium catalyst dry, first with equi-volume impregnating impregnate sodium chlorate solution, then and
The hydrochloric acid of 12mol/L reacts, and before hydrochloric acid is added, first dilutes hydrochloric acid with deionized water, the hydrochloric acid and deionized water
Volume ratio is 7: 20, and the hydrochloric acid is reacted with sodium chlorate solution generates Active Chlorine, is dried after standing；In the sodium chlorate solution
The molar ratio of palladium in sodium chlorate and palladium catalyst is 1: 1~2, the molar ratio of sodium chlorate and hydrochloric acid in the sodium chlorate solution
It is 1: 6~10；
Step 3: the pH value of the solution after step 2 reaction being adjusted to 4 or more, drying；
Step 4: the sample after step 3 drying is roasted.
2. the palladium catalyst regeneration method of high activity according to claim 1, which is characterized in that step 3 and step 4 it
Between, it further include that the mixed liquor of palladium chloride and sodium chloride is added, impregnates in the sample after step 3 drying, filtering adds water washing
Until mixed liquor not chloride ion-containing, drying.
3. the palladium catalyst regeneration method of high activity according to claim 1, which is characterized in that the step 1 it is specific
Operation are as follows: 50~70 DEG C of aromatic hydrocarbons of regenerated palladium catalyst will be needed to impregnate 3~6h, replace the primary virtue every 0.5h
Hydrocarbon；The palladium catalyst that aromatic hydrocarbons was impregnated, which is drained, impregnates 4~5h with 30~70 DEG C of alkaline solution, replaces primary institute every 0.5h
State alkaline solution；The palladium catalyst that alkaline solution was impregnated drains the water immersion with 30~90 DEG C, until being soaked with palladium catalyst
Aqueous solution be neutrality.
4. the palladium catalyst regeneration method of high activity according to claim 3, which is characterized in that the aromatic hydrocarbons is C9Aromatic hydrocarbons,
C10Aromatic hydrocarbons or C9Aromatic hydrocarbons and C10The mixture of aromatic hydrocarbons arbitrary proportion.
5. the palladium catalyst regeneration method of high activity according to claim 3, which is characterized in that the alkaline solution is hydrogen
Potassium oxide solution, sodium hydroxide solution, ammonium hydroxide, sodium carbonate liquor, sodium bicarbonate solution, solution of potassium carbonate and saleratus are molten
Liquid, the concentration of the alkaline solution are 0.05~0.30mol/L.
6. the palladium catalyst regeneration method of high activity according to claim 1, which is characterized in that carry out the step 1 it
Before screen out and need regenerated palladium catalyst, the method for screening are as follows: sieved, gone to waste and old palladium catalyst with the sieve of 10 mesh
Except partial size is in 2mm particle below.
7. the palladium catalyst regeneration method of high activity according to claim 1, which is characterized in that the temperature of the roasting is
500~550 DEG C, the time of the roasting is 2~4h.
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| CN113289694B (en) * | 2021-06-28 | 2023-04-28 | 广西田东达盛化工科技有限公司 | Method for regenerating palladium catalyst in anthraquinone process hydrogen peroxide production |
| CN114273022B (en) * | 2021-12-23 | 2023-06-16 | 江苏汇联铝业有限公司 | Filtering impurity-removing equipment for conveying high-purity alumina and implementation method thereof |
| CN115518655B (en) * | 2022-10-11 | 2023-09-15 | 中国成达工程有限公司 | Palladium catalyst recycling method and recycling system in succinic acid production |
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