CN107866223A - For catalyst of the acrylonitrile installation without thiamine process waste water - Google Patents
For catalyst of the acrylonitrile installation without thiamine process waste water Download PDFInfo
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- CN107866223A CN107866223A CN201610851848.4A CN201610851848A CN107866223A CN 107866223 A CN107866223 A CN 107866223A CN 201610851848 A CN201610851848 A CN 201610851848A CN 107866223 A CN107866223 A CN 107866223A
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/63—Platinum group metals with rare earths or actinides
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/727—Treatment of water, waste water, or sewage by oxidation using pure oxygen or oxygen rich gas
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/74—Treatment of water, waste water, or sewage by oxidation with air
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
- C02F2103/36—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
Abstract
The present invention relates to for catalyst of the acrylonitrile installation without thiamine process waste water, mainly solve the problems, such as that heterogeneous catalysis wet oxidation reaction catalyst initial activity is low in the prior art and stability difference.The present invention is by using for catalyst of the acrylonitrile installation without thiamine process waste water, including carrier and it is loaded in active component thereon, the carrier contains at least one of activated carbon and titanium dioxide, the active component is selected from the technical scheme that at least one of Ru, Pd, Pt, Rh and auxiliary agent are selected from least one of La, Ce, Nd and preferably solves the problem, available for CWO processing of the acrylonitrile installation without organic wastewater in thiamine process.
Description
Technical field
The present invention relates to for catalyst of the acrylonitrile installation without thiamine process waste water, more particularly to the wet type of the waste water
Aoxidize heterogeneous catalyst.
Background technology
Due to the characteristic (such as nontoxic, inexpensively, wide material sources etc.) of water, often by as reacting molten in chemical process
Agent, medium or thermophore etc. use, and therefore, inevitably destroy water quality.With flourishing for chemical industry, water
Body pollution is in ascendant trend, wherein pollution of the toxic organic compound to water body are particularly acute year by year.This pollutant has discharge capacity
Greatly, the features such as polluting wide and difficult for biological degradation, serious threat human lives, while also govern the hair of chemical industry
Exhibition.Therefore, how energy-efficient research is is located in reason industrial organic waste water, it has also become urgent problem to be solved.
The method of industrial wastewater treatment has its special scope of application.It is traditional biologic treating technique, photocatalysis, wet
Formula peroxide oxidation is only applicable to handle low concentration, the organic wastewater of no biotoxicity.Although burning method can handle high concentration
Organic wastewater, but burning need to consume great amount of fuel oil, high energy consumption；Meanwhile burning can produce such as NOx、COxHarmful gas such as, bioxin
Body, secondary pollution is caused to environment.Wet oxidation is that one kind processing to grow up the fifties in last century is poisonous, harmful, highly concentrated
Spend the method for organic wastewater.The method is under high-temperature and high-pressure conditions, using air or pure oxygen as oxidant, in the liquid phase by organic dirt
Dye thing is oxidized to CO2With the chemical process of the inorganic matter such as water or small organic molecule.This method has and has a wide range of application, handles effect
The advantages that rate is high, oxidation rate is fast, occupation area of equipment is small.Catalytic wet oxidation technology is in traditional wet-type oxidation technology
Efficient, the stable catalyst designed for waste water composition is added, so as to greatly improve oxidation efficiency, shortens reaction
Residence time, reduce the temperature needed for reaction, pressure and reduce production cost.
According to the attribute of catalyst, catalytic wet oxidation technology is divided into homogeneous and heterogeneous catalysis wet oxidation.Early stage grinds
Study carefully and be concentrated mainly on homogeneous catalyst, but due to catalyst be dissolved in it is useless in can cause secondary pollution, it is necessary to subsequent treatment so that
This method is phased out.Heterogeneous catalyst turns into study hotspot in recent years, and heterogeneous catalyst mainly has noble metal and metal oxide
Two major classes, wherein noble metal carrier catalyst have higher catalytic activity and stability, current such catalyst mostly with
TiO2、ZrO2、CeO2Or their composite oxides are carrier, and Ru, Rh, Pd, Ir, Pt, Au are supported on above-mentioned carrier.
It is disclosed directly below for precious metal catalyst Wet Oxidation Process patent：
CN1084496A discloses one kind and contains high-enriched organics and ammonia trade effluent wet oxidation cleaning catalyst, by expensive
Metal component (one of Ru, Rh, Pd, Ir, Pt) and rare earth element are supported in TiO2Upper composition, using double activated component co-impregnation or
The technology of preparing of sub-dip stain.CN1121322A discloses a kind of use in waste water treatment catalyst, its manufacture method and uses the catalysis
The method of wastewater treatment of agent, catalyst contain the oxide and/or composite oxides and this from iron, titanium and zirconium composition of manganese
The oxide and/or composite oxides of at least one metal selected in group, also contain noble metal if necessary.
Catalyst is through experiment in above patent, and activity and stability when handling acrylonitrile without thiamine process waste water are not
It is preferable.
The content of the invention
One of technical problems to be solved by the invention are in the prior art at the beginning of heterogeneous catalysis wet oxidation reaction catalyst
The problem of activity low and stability difference, there is provided a kind of new to be used for catalyst of the acrylonitrile installation without thiamine process waste water.This is urged
Agent, which is used for heterogeneous catalysis wet oxidation reaction processing acrylic nitrile waste water, has the advantages of initial activity height and high stability.
The two of the technical problems to be solved by the invention are to provide a kind of catalyst with solving used in one of technical problem
Corresponding preparation method.
The three of the technical problems to be solved by the invention are to provide a kind of catalyst used in by one of solution technical problem
Method for handling industrial wastewater.
To solve one of above-mentioned technical problem, the technical solution adopted by the present invention is as follows：
For catalyst of the acrylonitrile installation without thiamine process waste water, including carrier and it is loaded in active component thereon and helps
Agent, the carrier contain at least one of activated carbon and titanium dioxide, the active component in Ru, Pd, Pt, Rh at least one
Kind, the auxiliary agent is selected from least one of La, Ce, Nd.
In above-mentioned technical proposal, the carrier preferably contains activated carbon and titanium dioxide simultaneously, now activated carbon and titanium dioxide
Titanium has synergy to improving catalyst initial activity and stability.As non limiting example, the carrier can have such as
Lower structure type：
(1) complex carrier obtained after activated carbon and titanium dioxide simple physical mixed-forming；
(2) it is complex carrier of the core titanium dioxide as shell using activated carbon；
(3) it is core with the complex carrier of titanium dioxide shell using titanium dioxide Mixture of Activated Carbon.
From improve catalyst initial activity and stability meter by core of titanium dioxide Mixture of Activated Carbon using titanium dioxide as
The complex carrier best results of shell, it is thirdly activated carbon next to that being complex carrier of the core titanium dioxide as shell using activated carbon
With the complex carrier obtained after titanium dioxide simple physical mixed-forming.
In above-mentioned technical proposal, for being complex carrier of the core using titanium dioxide as shell using titanium dioxide Mixture of Activated Carbon
Situation, the ratio of specific core and shell is not particularly limited, and such as, but not limited to, the weight of core accounts for 40~95% by weight,
The weight of shell is 5~60%, and the ratio of titanium dioxide and activated carbon in core is it is not also specifically limited, such as, but not limited to titanium dioxide
Titanium is 30~95%, and activated carbon is 5~70%.
In above-mentioned technical proposal, with weight, the content of active component is preferably 0.01~2.0%, enters one
Step preferably 0.1~1.5%.
In above-mentioned technical proposal, with weight, the content of adjuvant component is preferably 0.01~10.0%, enters one
Step preferably 0.1~5.0%.
To solve the two of above-mentioned technical problem, technical scheme is as follows：Appoint in one of technical problem technical scheme
The preparation method of one catalyst, including：
(1) compound solution of the active component and adjuvant component and the carrier are mixed to get complex catalyst precursor
Thing；
(2) the compound state active component in catalyst precursors is reduced to simple substance with reducing agent.
In above-mentioned technical proposal, the specific method of step (2) reduction is not particularly limited, as long as can be the activity of compound state
Component is reduced to simple substance.For example, vapour phase reduction can be carried out to predecessor with gaseous reducing agent, reducing agent can also be used
Solution or liquid-phase reduction agent carry out liquid-phase reduction.The conventional gas that can include hydrogen of gaseous reducing agent, such as hydrogen, hydrogen
Gas-nitrogen mixture etc..The reducing agent of liquid-phase reduction can be hydrazine hydrate, formic acid or sodium formate etc..
In above-mentioned technical proposal, the compound of step (1) described active component is not particularly limited, and such as, but not limited to three
Ruthenic chloride, palladium bichloride, chlorine palladium acid, chloroplatinic acid, radium chloride etc..
In above-mentioned technical proposal, the compound of step (1) described adjuvant component is not particularly limited, such as, but not limited to nitre
Sour lanthanum, lanthanum chloride, lanthanum oxalate, lanthanum sulfate, cerium chloride, cerous nitrate, cerous sulfate, neodymium nitrate, Dineodymium trisulfate, neodymium chloride etc..
In above-mentioned technical proposal, when step (2) reduction uses the gas of hydrogen to carry out vapour phase reduction for gaseous reducing agent
When, the catalyst precursors, which preferably first pass through, to be dried and is calcined, and preferably 400~600 DEG C of the temperature of roasting, the time of roasting is excellent
Elect as 2~4.5 hours.
In above-mentioned technical proposal, when step (2) is reduced using hydrogen, reduction temperature is preferably 300~650 DEG C,
Further preferred 350~600 DEG C.
In above-mentioned technical proposal, the recovery time is preferably 1~5 hour, further preferred 2.5~4.5 hours.
In above-mentioned technical proposal, when the complex carrier using titanium dioxide Mixture of Activated Carbon is core using titanium dioxide as shell
When, the complex carrier is prepared using the method comprised the following steps：
1) by the water dirty solution containing titanium salt and activated carbon and ammoniacal liquor co-precipitation generation gelatinous mass, by filtering, washing, drying
It is dry, roasting, obtain the material 1；
2) shaping of material 1 obtains the core of the complex carrier；
3) TiO 2 sol is sprayed into the core surface described in step 2), is calcined, obtains the complex carrier.
In above-mentioned technical proposal, step 1) is described can be but not limited to Ti (SO containing titanium salt4)2, TiOSO4, TiCl4Deng.
In above-mentioned technical proposal, the addition of ammoniacal liquor and concentration are not particularly limited in step 1), as long as because by titaniferous
The water dirty solution of salt and activated carbon co-precipitation generation gelatinous mass, can be reasonable to reach this purpose those skilled in the art
Ammonia concn and dosage are selected, can reach the comparable technique effect of the present invention.As non-restrictive, ammoniacal liquor adds
It is 8.0~11.0 to enter amount to the pH value containing the water dirty solution containing titanium salt and activated carbon, is up to same in the specific embodiment of the invention
Than all co-precipitation generation gel occasions, being 9.8 with ammoniacal liquor regulation to pH.
In above-mentioned technical proposal, the temperature of step 1) roasting is preferably 150 DEG C~400 DEG C, and further preferred 200~350
℃；Roasting time is preferably 0.5~4 hour, further preferred 1~3 hour；The inert gas of calcination atmosphere preferred pair activated carbon
Atmosphere, such as, but not limited to nitrogen, argon gas etc..
In above-mentioned technical proposal, the forming method of step 2) is not particularly limited, and those skilled in the art can be used ripe
Those known, such as, but not limited to roller forming, compressing, extrusion molding etc..It is described to be extruded into as non limiting example
The method of type can use the method comprised the following steps to carry out：
In above-mentioned technical proposal, the sintering temperature after being sprayed in step 3) is preferably 400~950 DEG C, and roasting time is preferred
For 0.5~8 hour.
In above-mentioned technical proposal, described shaping assistant can be selected from organic formwork agent or extrusion aid.
As non limiting example, in above-mentioned technical proposal, the shaping assistant be selected from ethylenediamine, n-butylamine, pyrrolidines,
At least one of cetomacrogol 1000~5000, oxalic acid, citric acid, tartaric acid, sesbania powder.
Wet oxidizing catalyst described in the technical scheme of one of above-mentioned technical problem is in the processing of organic wastewater
Using.
One skilled in the art will appreciate that wet oxidizing catalyst is especially effective to the waste water of some special process processes, tool
There is very high specificity.In above-mentioned technical proposal, the wet oxidizing catalyst is particularly suitable for use in Acrylonitrile Production
The organic wastewater without thiamine process wet oxidation processing in application.
Processing method without thiamine process organic wastewater in Acrylonitrile Production, including propylene is produced with ammoxidation of propylene
Without thiamine process organic wastewater it is raw material caused by during nitrile, is mixed with the oxidant of the oxygen containing simple substance, equipped with above-mentioned technology
Waste water described in reaction treatment is carried out in the wet oxidation reactor of catalyst any one of the technical scheme of one of problem.It is main
Step is wanted to include：High ammonolysis product air-flow (6) from ammonia oxidation reactor out is in chilling tower (1) and the poor ammonium absorbing liquids of low COD
(17) contact absorbs unreacted ammonia in high ammonolysis product air-flow, obtains rich ammonium absorbing liquid (8) and low ammonolysis product air-flow (7)；By richness
Ammonium absorbing liquid (8) is interior through stripper stripping gas (9) stripping volatile organic component (10) in stripper (2), then is separating
Supernatant light component (11) is separated off in device (3) and is sunken to the heavy constituent (12) of lower floor, then in Analytic Tower (4)
Heated and Analytic Tower stripping gas (13) stripping obtains thick ammonia flow (15) and the poor ammonium absorbing liquids (14) of high COD, and the high poor ammoniums of COD are inhaled
Liquid (14) and oxygen-containing gas (16) are received after the middle reaction of the wet oxidation reactor (5) equipped with the catalyst of claim 1 or 2
Obtain the low poor ammonium absorbing liquids (17) of COD and return to the absorption that chilling tower (1) is used for unreacted ammonia；Thick ammonia flow (15) is after rectification process
Obtain stream of anhydrous ammonia (unlisted)；Wherein, contain in poor ammonium absorbing liquid in phosphoric acid, ammonium dihydrogen phosphate or sulfuric acid at least
A kind of absorbent.
In above-mentioned technical proposal, the oxidant is chosen as pure oxygen, air, oxygen-enriched air etc..
In above-mentioned technical proposal, the reaction temperature is preferably 220~300 DEG C.
In above-mentioned technical proposal, reaction pressure is preferably 5.0~12.0MPa.
In above-mentioned technical proposal, the volume ratio of oxygen and industrial wastewater is preferably 50~400.
In above-mentioned technical proposal, the COD of industrial wastewater is not particularly limited, such as, but not limited to 5000~100000mg/
L。
In above-mentioned technical proposal, residence time of the industrial wastewater in reactor is preferably 10~90 minutes.
In above-mentioned technical proposal, stripper stripping gas (9) and/or Analytic Tower stripping gas (13) are inert to stripping thing
Gas.
In above-mentioned technical proposal, the gas inert to stripping thing is at least one of water vapour, air and nitrogen.
In above-mentioned technical proposal, the heavy constituent (12) is high polymer and/or catalyst of ammoxidation for propylene powder.
In above-mentioned technical proposal, the high poor ammonium absorbing liquids (14) of COD are using water as solvent.
In above-mentioned technical proposal, Analytic Tower temperature is 150-250 DEG C.
Using technical scheme, industrial wastewater after oxygen mix with passing through the wet oxidation reaction equipped with catalyst
Device, reach more than 90% with initial reaction stage COD clearances, the stability of catalyst is also improved, and achieves preferable skill
Art effect.
Below by brief description of the drawings, the invention will be further elaborated with embodiment, but these embodiments are anyway
The scope of the present invention is not construed as limiting.
Brief description of the drawings
Fig. 1 is wet type of the wet oxidizing catalyst of the present invention in the organic wastewater without thiamine process of Acrylonitrile Production
The process chart of application in oxidation processes.
1 is chilling tower；2 be stripper；3 be separator；4 be Analytic Tower；5 be wet oxidation reactor；6 be that high ammonia produces
Product air-flow；7 be low ammonolysis product air-flow；8 be rich ammonium absorbing liquid；9 be stripper stripping gas；10 be volatile organic constituents；11 are
Light component；12 be heavy constituent；13 be Analytic Tower stripping gas；14 be the poor ammonium absorbing liquids of high COD；15 be thick ammonia flow；16 be oxygen-containing
Gas；17 be wet oxidation reaction after the low poor ammonium absorbing liquids of COD.
Wet oxidizing catalyst is poor in chilling tower 1 and low COD in the high ammonolysis product air-flow 6 from ammonia oxidation reactor out
The contact of ammonium absorbing liquid 17 absorbs unreacted ammonia in high ammonolysis product air-flow, obtains rich ammonium absorbing liquid 8 and low ammonolysis product air-flow 7；Will
Rich ammonium absorbing liquid 8 is interior through the stripping volatile organic component 10 of stripper stripping gas 9 in stripper 2, then in separator 3
It is separated off supernatant light component 11 and is sunken to the heavy constituent 12 of lower floor, then heated in Analytic Tower 4 and Analytic Tower
The stripping of stripping gas 13 obtains thick ammonia flow 15 and the poor ammonium absorbing liquids 14 of high COD, and the high poor ammonium absorbing liquids 14 of COD exist with oxygen-containing gas 16
The low poor ammonium absorbing liquids 17 of COD are obtained in wet oxidation reactor 5 equipped with wet oxidizing catalyst after wet oxidation reaction and return to urgency
Cold tower 1 is used for the absorption of unreacted ammonia；Thick ammonia flow 15 obtains stream of anhydrous ammonia (unlisted) after rectifying.
Embodiment
Waste water used in following examples and comparative example be acrylonitrile that COD value is 30000mg/l without thiamine process waste water,
Reactor is fixed bed reactors, and internal diameter is 14 millimeters, and reactor length is 600 millimeters.Continuously operation 24 is small for evaluating catalyst
The COD clearance initial activities constantly measured, it is activity eventually by the COD clearances measured when continuously running 300 hours, by front and rear
Activity change calculates active reduced rate, and formula is as follows：
Active reduced rate, %=[(initial activity-end activity)/initial activity] × 100%
Evaluation index using active reduced rate as catalyst stability, the value is lower, and explanation catalyst performance is more stable,
Vice versa.
【Embodiment 1】
Catalyst preparation：
Step 1)
Prepare 0.3mol/l TiOSO4Aqueous solution 2000ml, 12g activity powdered carbons are added, 0.6mol/l ammoniacal liquor is instilled this
Dirty solution co-precipitation generation gelatinous mass, by filtering, washing, drying, be calcined 2 hours under 300 DEG C of nitrogen atmospheres, is made and answers
Close carrier core powder；
Step 2)
45g complex carrier cores powder, 0.1g n-butylamines and 0.1g oxalic acid are mixed, by kneading, extrusion, pill, dried
Cheng Hou, the core of complex carrier is made；The colloidal sol that 50g titania weights content is 10% is sprayed on the core of complex carrier,
It is calcined 4 hours at 850 DEG C after drying, complex carrier is made；
Step 3)
50g complex carriers are impregnated in the cerous nitrate solution of the Ce containing 1.30g.6h is impregnated at room temperature, is dried, 350 DEG C
2.5h is calcined, obtains catalyst precursor；
Step 4)
Catalyst precursor is impregnated in the RuCl of the Ru containing 0.50g3In solution.6h is impregnated at room temperature, is dried, 480 DEG C
2.5h is calcined, then obtains finished catalyst within 3 hours with hydrogen reducing at 400 DEG C；
Catalyst test：
Catalyst obtained by above-mentioned preparation is loaded into wet oxidation reactor, waste water is with carrying out catalytic wet oxygen after oxygen mix
Change reaction, waste water is 40min in the residence time of the effective section of reactor, and reaction temperature is 280 DEG C, reaction pressure 9MPa, oxygen
Gas is 100 with wastewater volume ratio.
【Embodiment 2】
Catalyst preparation：
Step 1)
Prepare 0.3mol/l TiOSO4Aqueous solution 2000ml, 0.6mol/l ammoniacal liquor is instilled into the co-precipitation generation of this dirty solution
Gelatinous mass, by filtering, washing, drying, it is calcined 2 hours under 300 DEG C of nitrogen atmospheres, titanium dioxide powder is made；
Step 2)
41g titanium dioxide powders, 9g activity powdered carbon, 0.1g n-butylamines and 0.1g oxalic acid are mixed, by kneading, extrusion, system
After ball, drying process, it is calcined 4 hours at 850 DEG C, complex carrier is made；
Step 3)
50g complex carriers are impregnated in the cerous nitrate solution of the Ce containing 1.30g.6h is impregnated at room temperature, is dried, 350 DEG C
2.5h is calcined, obtains catalyst precursor；
Step 4)
Catalyst precursor is impregnated in the RuCl of the Ru containing 0.50g3In solution.6h is impregnated at room temperature, is dried, 480 DEG C
2.5h is calcined, then obtains finished catalyst within 3 hours with hydrogen reducing at 400 DEG C；
Catalyst test：
Catalyst obtained by above-mentioned preparation is loaded into wet oxidation reactor, waste water is with carrying out catalytic wet oxygen after oxygen mix
Change reaction, waste water is 40min in the residence time of the effective section of reactor, and reaction temperature is 280 DEG C, reaction pressure 9MPa, oxygen
Gas is 100 with wastewater volume ratio.
【Embodiment 3】
Step 1)
9g activity powdered carbon, 0.02g n-butylamines and 0.02g oxalic acid are mixed, by kneading, extrusion, pill, drying process
Afterwards, it is calcined 2 hours under 300 DEG C of nitrogen atmospheres, the core of complex carrier is made；
Step 2)
The colloidal sol that 410g titania weights content is 10% is sprayed on the core of 9g complex carriers several times, after drying
It is calcined 4 hours at 850 DEG C, complex carrier is made；
Step 3)
50g complex carriers are impregnated in the cerous nitrate solution of the Ce containing 1.30g.6h is impregnated at room temperature, is dried, 350 DEG C
2.5h is calcined, obtains catalyst precursor；
Step 4)
Catalyst precursor is impregnated in the RuCl of the Ru containing 0.50g3In solution.6h is impregnated at room temperature, is dried, 480 DEG C
2.5h is calcined, then obtains finished catalyst within 3 hours with hydrogen reducing at 400 DEG C；
Catalyst test：
Catalyst obtained by above-mentioned preparation is loaded into wet oxidation reactor, waste water is with carrying out catalytic wet oxygen after oxygen mix
Change reaction, waste water is 40min in the residence time of the effective section of reactor, and reaction temperature is 280 DEG C, reaction pressure 9MPa, oxygen
Gas is 100 with wastewater volume ratio.
【Comparative example 1】
Catalyst preparation：
Step 1)
Prepare 0.3mol/l TiOSO4Aqueous solution 2000ml, 0.6mol/l ammoniacal liquor is instilled into the co-precipitation generation of this dirty solution
Gelatinous mass, by filtering, washing, drying, titanium dioxide powder is made；
Step 2)
50g titanium dioxide powders, 0.1g n-butylamines and 0.1g oxalic acid are mixed, by kneading, extrusion, pill, drying process
Afterwards, it is calcined 4 hours at 850 DEG C, carrier is made；
Step 3)
50g complex carriers are impregnated in the cerous nitrate solution of the Ce containing 1.30g.6h is impregnated at room temperature, is dried, 350 DEG C
2.5h is calcined, obtains catalyst precursor；
Step 4)
Catalyst precursor is impregnated in the RuCl of the Ru containing 0.50g3In solution.6h is impregnated at room temperature, is dried, 480 DEG C
2.5h is calcined, then obtains finished catalyst within 3 hours with hydrogen reducing at 400 DEG C；
Catalyst test：
Catalyst obtained by above-mentioned preparation is loaded into wet oxidation reactor, waste water is with carrying out catalytic wet oxygen after oxygen mix
Change reaction, waste water is 40min in the residence time of the effective section of reactor, and reaction temperature is 280 DEG C, reaction pressure 9MPa, oxygen
Gas is 100 with wastewater volume ratio.
【Comparative example 2】
Catalyst preparation：
Step 1)
By 50g activity powdered carbons, 0.1g n-butylamines and the mixing of 0.1g oxalic acid, by kneading, extrusion, pill, drying process
Afterwards, it is calcined 2 hours under 300 DEG C of nitrogen atmospheres, absorbent charcoal carrier is made；
Step 2)
50g absorbent charcoal carriers are impregnated in the cerous nitrate solution of the Ce containing 1.30g.6h is impregnated at room temperature, is dried, 350
DEG C roasting 2.5h, obtain catalyst precursor；
Step 3)
Catalyst precursor is impregnated in the RuCl of the Ru containing 0.50g3In solution.6h is impregnated at room temperature, is dried, 480 DEG C
2.5h is calcined, then obtains finished catalyst within 3 hours with hydrogen reducing at 400 DEG C；
Catalyst test：
Catalyst obtained by above-mentioned preparation is loaded into wet oxidation reactor, waste water is with carrying out catalytic wet oxygen after oxygen mix
Change reaction, waste water is 40min in the residence time of the effective section of reactor, and reaction temperature is 280 DEG C, reaction pressure 9MPa, oxygen
Gas is 100 with wastewater volume ratio.
【Embodiment 4】
Catalyst preparation：
Step 1)
Prepare 0.3mol/l TiOSO4Aqueous solution 2000ml, 12g activity powdered carbons are added, 0.6mol/l ammoniacal liquor is instilled this
Dirty solution co-precipitation generation gelatinous mass, by filtering, washing, drying, be calcined 4 hours under 150 DEG C of nitrogen atmospheres, is made and answers
Close carrier core powder；
Step 2)
40g complex carrier cores powder, 0.1g ethylenediamines and 0.1g oxalic acid are mixed, by kneading, extrusion, pill, dried
Cheng Hou, the core of complex carrier is made；The colloidal sol that 100g titania weights content is 10% is sprayed on the core of complex carrier,
It is calcined 3 hours at 400 DEG C after drying, complex carrier is made；
Step 3)
50g complex carriers are impregnated in the lanthanum nitrate hexahydrate of the La containing 0.78g.6h is impregnated at room temperature, is dried, 300 DEG C
2.5h is calcined, obtains catalyst precursor；
Step 4)
Catalyst precursor is impregnated in the H of the Pt containing 0.25g2PtCl6In solution.6h is impregnated at room temperature, is dried, 400
DEG C of 480 DEG C roasting 2h 2.5h, then obtain finished catalyst in 2 hours at 300 DEG C 400 DEG C with hydrogen reducing；
Catalyst test：
Catalyst obtained by above-mentioned preparation is loaded into wet oxidation reactor, waste water is with carrying out catalytic wet oxygen after oxygen mix
Change reaction, waste water is 40min in the residence time of the effective section of reactor, and reaction temperature is 280 DEG C, reaction pressure 9MPa, oxygen
Gas is 100 with wastewater volume ratio.
【Embodiment 5】
Catalyst preparation：
Step 1)
Prepare 0.3mol/l TiOSO4Aqueous solution 2000ml, 12g activity powdered carbons are added, 0.6mol/l ammoniacal liquor is instilled this
Dirty solution co-precipitation generation gelatinous mass, by filtering, washing, drying, be calcined 0.5 hour under 400 DEG C of nitrogen atmospheres, obtained
Complex carrier core powder；
Step 2)
35g complex carrier cores powder, 0.1g n-butylamines and 0.1g sesbania powders are mixed, by kneading, extrusion, pill, drying
After process, the core of complex carrier is made；The colloidal sol that 150g titania weights content is 10% is sprayed on to the core of complex carrier
On, it is calcined 0.5 hour at 950 DEG C after drying, complex carrier is made；
Step 3)
50g complex carriers are impregnated in the lanthanum nitrate hexahydrate of the La containing 1.90g.6h is impregnated at room temperature, is dried, 350 DEG C
2.5h is calcined, obtains catalyst precursor；
Step 4)
Catalyst precursor is impregnated in the PdCl of the Pd containing 0.61g2In solution.6h is impregnated at room temperature, is dried, 600 DEG C
4h is calcined, then obtains finished catalyst within 2 hours with hydrogen reducing at 650 DEG C；
Catalyst test：
Catalyst obtained by above-mentioned preparation is loaded into wet oxidation reactor, waste water is with carrying out catalytic wet oxygen after oxygen mix
Change reaction, waste water is 60min in the residence time of the effective section of reactor, and reaction temperature is 280 DEG C, reaction pressure 9MPa, oxygen
Gas is 150 with wastewater volume ratio.
【Embodiment 6】
Catalyst preparation：
Step 1)
Prepare 0.3mol/l TiOSO4Aqueous solution 1500ml, 24g activity powdered carbons are added, 0.6mol/l ammoniacal liquor is instilled this
Dirty solution co-precipitation generation gelatinous mass, by filtering, washing, drying, be calcined 3 hours under 250 DEG C of nitrogen atmospheres, is made and answers
Close carrier core powder；
Step 2)
45g complex carrier cores powder, 0.1g pyrrolidines and 0.1g sesbania powders are mixed, by kneading, extrusion, pill, drying
After process, the core of complex carrier is made；The colloidal sol that 50g titania weights content is 10% is sprayed on to the core of complex carrier
On, it is calcined 6 hours at 750 DEG C after drying, complex carrier is made；
Step 3)
50g complex carriers are impregnated in the neodymium nitrate solution of the Nd containing 1.10g.6h is impregnated at room temperature, is dried, 350 DEG C
2.5h is calcined, obtains catalyst precursor；
Step 4)
Catalyst precursor is impregnated in the H of the Pt containing 0.40g2PtCl6In solution.6h is impregnated at room temperature, is dried, 500
DEG C roasting 4h, then obtain finished catalyst within 4 hours with hydrogen reducing at 500 DEG C；
Catalyst test：
Catalyst obtained by above-mentioned preparation is loaded into wet oxidation reactor, waste water is with carrying out catalytic wet oxygen after oxygen mix
Change reaction, waste water is 60min in the residence time of the effective section of reactor, and reaction temperature is 220 DEG C, reaction pressure 6MPa, oxygen
Gas is 150 with wastewater volume ratio.
【Embodiment 7】
Catalyst preparation：
Step 1)
Prepare 0.3mol/l TiOSO4Aqueous solution 1250ml, 30g activity powdered carbons are added, 0.6mol/l ammoniacal liquor is instilled this
Dirty solution co-precipitation generation gelatinous mass, by filtering, washing, drying, be calcined 3 hours under 250 DEG C of nitrogen atmospheres, is made and answers
Close carrier core powder；
Step 2)
By 45g complex carrier cores powder, 0.1g polyethylene glycol 2000s and 0.1g oxalic acid mix, by kneading, extrusion, pill,
After drying process, the core of complex carrier is made；The colloidal sol that 50g titania weights content is 10% is sprayed on complex carrier
On core, it is calcined 5 hours at 800 DEG C after drying, complex carrier is made；
Step 3)
50g complex carriers are impregnated in the cerous nitrate solution of the Ce containing 2.0g.6h is impregnated at room temperature, is dried, 350 DEG C
2.5h is calcined, obtains catalyst precursor；
Step 4)
Catalyst precursor is impregnated in the RuCl of the Ru containing 0.60g3In solution.6h is impregnated at room temperature, is dried, 450 DEG C
3h is calcined, then obtains finished catalyst within 2 hours with hydrogen reducing at 600 DEG C；
Catalyst test：
Catalyst obtained by above-mentioned preparation is loaded into wet oxidation reactor, waste water is with carrying out catalytic wet oxygen after oxygen mix
Change reaction, waste water is 80min in the residence time of the effective section of reactor, and reaction temperature is 280 DEG C, reaction pressure 9MPa, oxygen
Gas is 100 with wastewater volume ratio.
【Embodiment 8】
Catalyst preparation：
Step 1)
Prepare 0.3mol/l TiOSO4Aqueous solution 1375ml, 27g activity powdered carbons are added, 0.6mol/l ammoniacal liquor is instilled this
Dirty solution co-precipitation generation gelatinous mass, by filtering, washing, drying, be calcined 4 hours under 200 DEG C of nitrogen atmospheres, is made and answers
Close carrier core powder；
Step 2)
45g complex carrier cores powder, 0.1g ethylenediamines and 0.1g citric acids are mixed, by kneading, extrusion, pill, drying
After process, the core of complex carrier is made；The colloidal sol that 50g titania weights content is 10% is sprayed on to the core of complex carrier
On, it is calcined 5 hours at 850 DEG C after drying, complex carrier is made；
Step 3)
50g complex carriers are impregnated in the cerous nitrate solution of the Ce containing 2.50g.6h is impregnated at room temperature, is dried, 350 DEG C
2.5h is calcined, obtains catalyst precursor；
Step 4)
Catalyst precursor is impregnated in the RhCl of the Rh containing 0.90g3In solution.6h is impregnated at room temperature, is dried, 450 DEG C
2.5h is calcined, then obtains finished catalyst within 3 hours with hydrogen reducing at 400 DEG C；
Catalyst test：
Catalyst obtained by above-mentioned preparation is loaded into wet oxidation reactor, waste water is with carrying out catalytic wet oxygen after oxygen mix
Change reaction, waste water is 40min in the residence time of the effective section of reactor, and reaction temperature is 300 DEG C, reaction pressure 10MPa, oxygen
Gas is 200 with wastewater volume ratio.
【Embodiment 9】
Catalyst preparation：
Step 1)
Prepare 0.3mol/l TiOSO4Aqueous solution 1875ml, 15g activity powdered carbons are added, 0.6mol/l ammoniacal liquor is instilled this
Dirty solution co-precipitation generation gelatinous mass, by filtering, washing, drying, be calcined 4 hours under 250 DEG C of nitrogen atmospheres, is made and answers
Close carrier core powder；
Step 2)
45g complex carrier cores powder, 0.1g n-butylamines and 0.1g oxalic acid are mixed, by kneading, extrusion, pill, dried
Cheng Hou, the core of complex carrier is made；The colloidal sol that 50g titania weights content is 10% is sprayed on the core of complex carrier,
It is calcined 7 hours at 750 DEG C after drying, complex carrier is made；
Step 3)
50g complex carriers are impregnated in the lanthanum nitrate hexahydrate of the La containing 1.50g.6h is impregnated at room temperature, is dried, 400 DEG C
2.5h is calcined, obtains catalyst precursor；
Step 4)
Catalyst precursor is impregnated in the RuCl of the Ru containing 0.71g3In solution.6h is impregnated at room temperature, is dried, 550 DEG C
2.5h is calcined, then obtains finished catalyst within 3 hours with hydrogen reducing at 500 DEG C；
Catalyst test：
Catalyst obtained by above-mentioned preparation is loaded into wet oxidation reactor, waste water is with carrying out catalytic wet oxygen after oxygen mix
Change reaction, waste water is 30min in the residence time of the effective section of reactor, and reaction temperature is 275 DEG C, reaction pressure 8MPa, oxygen
Gas is 300 with wastewater volume ratio.
【Embodiment 10】
Catalyst preparation：
Step 1)
Prepare 0.3mol/l TiOSO4Aqueous solution 2000ml, 12g activity powdered carbons are added, 0.6mol/l ammoniacal liquor is instilled this
Dirty solution co-precipitation generation gelatinous mass, by filtering, washing, drying, be calcined 3 hours under 280 DEG C of nitrogen atmospheres, is made and answers
Close carrier core powder；
Step 2)
45g complex carrier cores powder, 0.1g ethylenediamines and 0.1g sesbania powders are mixed, by kneading, extrusion, pill, drying
After process, the core of complex carrier is made；The colloidal sol that 50g titania weights content is 10% is sprayed on to the core of complex carrier
On, it is calcined 4 hours at 900 DEG C after drying, complex carrier is made；
Step 3)
50g complex carriers are impregnated in the cerous nitrate solution of the Ce containing 1.50g.6h is impregnated at room temperature, is dried, 350 DEG C
2.5h is calcined, obtains catalyst precursor；
Step 4)
Catalyst precursor is impregnated in the H of the Pt containing 0.35g2PtCl6In solution.6h is impregnated at room temperature, is dried, 400
DEG C roasting 3h, then obtain finished catalyst within 4 hours with hydrogen reducing at 400 DEG C；
Catalyst test：
Catalyst obtained by above-mentioned preparation is loaded into wet oxidation reactor, waste water is with carrying out catalytic wet oxygen after oxygen mix
Change reaction, waste water is 40min in the residence time of the effective section of reactor, and reaction temperature is 280 DEG C, reaction pressure 9MPa, oxygen
Gas is 250 with wastewater volume ratio.
Table 1
Claims (10)
1. be used for catalyst of the acrylonitrile installation without thiamine process waste water, including carrier and it is loaded in active component thereon and helps
Agent, the carrier contain at least one of activated carbon and titanium dioxide, the active component in Ru, Pd, Pt, Rh at least one
Kind, the auxiliary agent is selected from least one of La, Ce, Nd.
2. catalyst according to claim 1, it is characterized in that, with weight, the content of active component is
0.01~2.0%.
3. catalyst according to claim 1, it is characterized in that, with weight, the content of adjuvant component is
0.01~10.0%.
4. the preparation method of wet oxidizing catalyst described in claim 1, including：
(1) compound solution of the active component and adjuvant component and the carrier are mixed to get catalyst precursors；
(2) the compound state active component in catalyst precursors is reduced to simple substance with reducing agent.
5. preparation method according to claim 4, it is characterized in that step (2) is reduced to liquid-phase reduction.
6. preparation method according to claim 5, it is characterized in that reduction that liquid-phase reduction uses and for hydrazine hydrate, formic acid or
The alkali metal salt of formic acid.
7. preparation method according to claim 4, it is characterized in that step (2) is reduced to vapour phase reduction.
8. preparation method according to claim 7, it is characterized in that the vapour phase reduction agent that vapour phase reduction uses is including hydrogen
Gas.
9. preparation method according to claim 8, it is characterized in that reduction temperature is 300~650 DEG C.
10. application of the wet oxidizing catalyst in the wet oxidation processing of organic wastewater described in claim 1.
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| US6423236B1 (en) * | 1999-01-07 | 2002-07-23 | Nippon Shokubai Co., Ltd. | Method for treating waste water |
| CN103041811A (en) * | 2011-10-17 | 2013-04-17 | 中国石油化工股份有限公司 | Preparation method of catalytic wet oxidation catalyst and treatment method of organic wastewater |
| CN104043452A (en) * | 2013-03-13 | 2014-09-17 | 中国石油化工股份有限公司 | Heterogeneous catalytic wet oxidation catalyst using active carbon as carrier and preparation method thereof |
| CN104667985A (en) * | 2013-11-29 | 2015-06-03 | 中国石油化工股份有限公司 | Catalytic wet oxidation catalyst and preparation method thereof |
| CN105080540A (en) * | 2014-05-14 | 2015-11-25 | 中国石油化工股份有限公司 | Wet oxidation catalyst and preparation method thereof |
| CN105597740A (en) * | 2014-11-20 | 2016-05-25 | 中国石油化工股份有限公司 | Heterogeneous catalysis wet oxidation catalyst and preparation method thereof |
-
2016
- 2016-09-26 CN CN201610851848.4A patent/CN107866223B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6423236B1 (en) * | 1999-01-07 | 2002-07-23 | Nippon Shokubai Co., Ltd. | Method for treating waste water |
| CN103041811A (en) * | 2011-10-17 | 2013-04-17 | 中国石油化工股份有限公司 | Preparation method of catalytic wet oxidation catalyst and treatment method of organic wastewater |
| CN104043452A (en) * | 2013-03-13 | 2014-09-17 | 中国石油化工股份有限公司 | Heterogeneous catalytic wet oxidation catalyst using active carbon as carrier and preparation method thereof |
| CN104667985A (en) * | 2013-11-29 | 2015-06-03 | 中国石油化工股份有限公司 | Catalytic wet oxidation catalyst and preparation method thereof |
| CN105080540A (en) * | 2014-05-14 | 2015-11-25 | 中国石油化工股份有限公司 | Wet oxidation catalyst and preparation method thereof |
| CN105597740A (en) * | 2014-11-20 | 2016-05-25 | 中国石油化工股份有限公司 | Heterogeneous catalysis wet oxidation catalyst and preparation method thereof |
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