CN106560239B - A kind of catalyst and its preparation method and application of catalytic chlorination hydroxide - Google Patents
A kind of catalyst and its preparation method and application of catalytic chlorination hydroxide Download PDFInfo
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- CN106560239B CN106560239B CN201610556565.7A CN201610556565A CN106560239B CN 106560239 B CN106560239 B CN 106560239B CN 201610556565 A CN201610556565 A CN 201610556565A CN 106560239 B CN106560239 B CN 106560239B
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- 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
- B01J23/005—Spinels
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- 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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/26—Chromium
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- 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/86—Chromium
- B01J23/864—Cobalt and chromium
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/036—Precipitation; Co-precipitation to form a gel or a cogel
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B7/00—Halogens; Halogen acids
- C01B7/01—Chlorine; Hydrogen chloride
- C01B7/03—Preparation from chlorides
- C01B7/04—Preparation of chlorine from hydrogen chloride
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G37/00—Compounds of chromium
- C01G37/14—Chromates; Bichromates
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/30—Three-dimensional structures
- C01P2002/32—Three-dimensional structures spinel-type (AB2O4)
Abstract
The invention discloses a kind of catalyst of catalytic chlorination hydroxide, are MCr comprising chemical formula2O4Chromate at least one；Wherein, M is selected from Co or Zn.In addition, the present invention also provides the preparation method of the catalyst and its applications in catalytic chlorination hydroxide.Catalyst of the invention has the characteristics that high activity, high stability, nontoxic and at low cost, can be used for the catalyzed conversion of catalytic oxidation of hydrogen chloride for preparing chlorine gas or industrial chlorinations hydrogen exhaust gas.
Description
Technical field:
The invention belongs to catalyst fields and field of environment protection, and in particular to a kind of catalyst of catalytic chlorination hydroxide
And its preparation method and application.
Background technique:
Chlorine is a kind of important Elementary Chemical Industry raw material, is widely used in polyurethane, organosilicon, epoxy resin, chlorination rubber
The new materials industry such as glue, chlorinated high polymers, chlorinated hydrocabon is applied to the new energy industries such as polysilicon manufacture, applied to disinfectant, washes
Wash the life Fine Chemicals such as agent, food additives, cosmetic additive, be applied to synthetic glycerine, chlorobenzene series, monoxone,
Benzyl chloride, etc. pesticides pharmaceuticals industry, and be applied to the industries such as papermaking, weaving, metallurgy and petrochemical industry.
In largely consumption chlorine industry, occur two serious restraining factors in the use of chlorine.Such as chlorine industry
In, the power consumption superelevation of one ton of chlorine of every production, and the outlet of the hydrogen chloride of by-product or hydrochloric acid is difficult.And chloration hydro-oxidation system
Making chlorine is the fine thinking for solving both of these problems.From the point of view of the development of nearest decades, catalytic oxidation is most effective
Solution, the catalytic oxidation especially reacted via Deacon, due to the low feature of easy to operate, equipment cost, most
Industrialization potential.
Deacon reaction is the reaction by chloration hydro-oxidation at chlorine in the presence of a catalyst.The type of catalyst is straight
Connect the conversion ratio for influencing Deacon reaction hydrogen chloride.Catalyst used in Deacon reaction at present mainly uses chromium, copper and ruthenium
Equal metallic elements.Wherein, ruthenium catalyst limits its extensive use due to expensive.Cu-series catalyst is only at high temperature
With greater activity；Although chromium-based catalysts have preferable low temperature active, stability is poor, and due to the poison of Cr VI
Property, it causes serious pollution to the environment.Therefore, the copper system of higher performance is developed, chromium-based catalysts are still current research emphasis.
Disclosed in EP0184413 using chromium oxide as the method for catalyst oxidation chlorination hydrogen, but catalyst activity compared with
Low, the conversion ratio of hydrogen chloride is 70% or so.CN85109387A discloses a kind of utilization precipitation method synthesis group based on chromium oxide
The catalyst divided, although activity can reach 80% or so.But these catalyst stabilities are not high, because of chromium and chlorine pole
Easily form low-boiling chromium oxychloride (CrO2Cl2) and hydroxide oxygen chromium (CrO2(OH)2).Higher reaction temperature or long-time
Reaction is easy to make catalyst inactivation.US5707919 discloses a kind of improved method of chromium oxide catalyst, be added a small amount of mantoquita,
Sylvite and rare earth metal are as auxiliary agent, and prepared catalyst activity is high, and stability is improved, and hydrogen chloride conversion ratio reaches
85.2%.CN104785271A disclose it is a kind of using comminution granulation prepare with chromium oxide be main constituent catalysts, addition copper,
The auxiliary agents such as boron, alkali metal, rare earth metal, using Aluminum sol, silica solution as carrier.Catalyst activity is high, and stability is preferable,
The conversion ratio of hydrogen chloride has certain anti-caking and preferable mechanical strength 80% or more, can be used for fluidizing
Bed reactor.But since Cr VI has larger toxicity, problem of environmental pollution existing for chromium oxide catalyst limits it in work
Application in industry.
In conclusion arriving mesh although domestic and international researcher is made that many effort in terms of improving chromium-based catalysts
Before until, the chloration hydro-oxidation technique based on chromium-based catalysts still be not implemented industrialization.Therefore, prepare high activity, high stability,
Nontoxic novel the catalytic oxidation of hydrogen chloride catalyst, is still of great significance.
Summary of the invention:
In order to overcome numerous deficiencies in the prior art, the present invention is intended to provide a kind of catalytic activity is high, stability is high, poison
The catalyst of the small catalytic chlorination hydroxide of property.
In addition, the present invention also provides the preparation method of the catalyst and its applications in catalytic chlorination hydroxide.
A kind of catalyst of catalytic chlorination hydroxide is MCr comprising chemical formula2O4Chromate at least one；Wherein, M
Selected from Co or Zn.
In the present invention, the catalyst include cobalt-chromate, in zinc chromate at least one of.Catalyst of the invention
Have the characteristics that high activity, high stability, nontoxic and at low cost, be not only suitable for extensive catalytic oxidation of hydrogen chloride for preparing chlorine gas,
Catalysis oxidation suitable for industrial chlorinations hydrogen exhaust gas converts.
Preferably, the chromate has spinel structure in the catalyst.
The MCr2O4In, M is Co the or Zn metal ion of divalent.
Preferably, the catalyst is cobalt-chromate.Present invention applicant's discovery, using cobalt-chromate catalytic chlorination hydrogen-oxygen
Change prepares the performances such as the catalytic performance of chlorine, stability and is further promoted.
Preferably, in chromate, the molar ratio of M and Cr are 1: 1~1: 4 in the catalyst.
Further preferably, in the catalyst, in chromate, the molar ratio of M and Cr are 1: 2~1: 3.
More preferably, in chromate, the molar ratio of M and Cr are 1: 2 in the catalyst.The present inventors have additionally discovered that
Under the ratio, the catalyst is the chromate for being spinel structure, and the catalytic oxidation activity of HCl is stronger, and catalyst
Stability also has greatly improved.Catalytic activity can decline when M excess, conversely, when Cr excess catalyst it is steady
It is qualitative to decline.
The inventors discovered that the catalyst is preferably specific surface area 15-30m2/g；Crystal form is spinel-type, crystalline substance
Body particle size is in 10~50nm.Under the optimum condition, the stability of catalyst is strong, catalytic activity is high.
Further preferably, that the catalyst is preferably specific surface area 25-30m2/g；Crystal particle diameter size 15~
30nm。
The catalyst using the chromate as principal active component, chromate content more high catalytic activity more
It is high；The inventors discovered that the weight percent of catalytic active component cobalt-chromate and/or zinc chromate is greater than in the catalyst
Or it is equal to 50%.Can have good catalytic activity and stability in the chromate of the weight percent.
Further preferably, in the catalyst, the weight percent of the chromate is greater than or equal to 90%.
The present invention also provides application of the catalyst described in one kind in catalytic chlorination hydroxide, oxygen, hydrogen chloride with
The catalyst contact, carries out catalytic oxidation and chlorine is made.
Preferably, oxygen, hydrogen chloride and the catalyst are contacted, the pipe of serialization is carried out in the application
Formula or bed catalysis reaction, are made chlorine.
Serialization catalysis reaction preferably uses gas phase continuous fixed bed reaction or continuous device.
In application of the present invention, such as it can react under normal pressure.
Preferably, the temperature of catalytic oxidation is 360~500 DEG C.
Further preferably, catalytic oxidation temperature is 380~480 DEG C.
More preferably, catalytic oxidation temperature is 400~450 DEG C；Preferred is 430 DEG C.
Preferably, the molar ratio of hydrogen chloride and oxygen is 4: 1~1: 4.
Further preferably, the molar ratio of hydrogen chloride and oxygen is 0.5~2.More preferably, the molar ratio of hydrogen chloride and oxygen
It is 0.5~1.Preferably, the molar ratio of hydrogen chloride and oxygen is 0.5.
More preferably, the molar ratio of hydrogen chloride and oxygen is 0.5~1；Reaction temperature is 400~450 DEG C.
500~10000h of volume space velocity of oxygen and chlorine hydride mixed gas body-1, preferably 3000~6000h-1。
Existing fluidized bed reaction catalysis can also be used when granularity is at 20nm~5 μm in catalyst of the present invention
Preparing chlorine by oxidizing hydrogen chloride.
The invention also includes the preparation method of the catalyst described in one kind, the preparation method using sol-gel method or
The precipitation method:
The sol-gel method includes: that M presoma, Cr presoma, citric acid are dispersed in water to obtain starting aqueous solution；
Then mixed again with water soluble polymer, hydro-thermal reaction forms gel, then through drying, roast, be ground up, sieved obtained institute
State catalyst；
The precipitation method include: that M presoma, Cr presoma are dispersed in water to obtain mixed aqueous solution, to mixed aqueous solution
In add lye and carry out precipitation reaction, then precipitated product is washed, is dried, is roasted, is ground up, sieved the catalyst is made；
In the sol-gel method and the precipitation method, M presoma is water-soluble cobalt compound, in zinc compound
It is at least one；Cr presoma is the water soluble compound of chromium.
Chloride, nitrate, the acetate of the aqueous cobalt compound, zinc compound selected from corresponding metal etc. is solvable
Property salt or organic coordination compounds.
Preferably, the cobalt compound is selected from least one of cobalt chloride, cobalt nitrate, cobalt acetate.
Preferably, the zinc compound is selected from least one of zinc chloride, zinc nitrate, zinc acetate.
Preferably, the chromium compound is selected from least one of chromium chloride, chromic nitrate, chromium acetate.
The water soluble polymer be preferably polyethylene glycol, polyvinyl alcohol, in polyvinylpyrrolidone extremely
Few one kind.
In the sol-gel method, first the M presoma, Cr presoma, citric acid are dissolved in aqueous solution and must originated
Aqueous solution, the inventors discovered that, the concentration of M presoma, Cr presoma, citric acid in the starting aqueous solution urges preparation
Activity and the stability tool of agent have a certain impact；Preferably, in the starting aqueous solution；The molar concentration of Cr is 0.1
~1moL/L.Under the concentration of the chromium of the starting, preparation section is high-efficient, and the catalytic performance of catalyst obtained is mentioned
It rises.The molar concentration of M and according to the M/Cr molar ratio of the catalyst convert.For example, the molar ratio of M and Cr is 1: 1~1:
4；Preferably 1: 2~1: 3, preferred 1: 2.
Under the molar concentration of the preferred Cr, preferably, in the starting aqueous solution, the concentration of citric acid is
0.1moL/L~2moL/L.Further preferably, in sol-gel method, in the starting aqueous solution, the concentration of citric acid is
0.2moL/L~1moL/L.
In the sol-gel method, the dosage of water soluble polymer is to guarantee to be formed good gel
Preferably；Whether the dosage of water soluble polymer has an impact to catalyst obtained, if so, adding for polymer please be supplemented
Amount, for example, the dosage of the water soluble polymer is 0.4~0.8 times of Cr forerunner's body weight.It is water-soluble
Property high molecular polymer play dispersing agent, can be used aqueous solution form addition, mass fraction is, for example, 5%~15%.
In the sol-gel method, the temperature of water-bath is 50~90 DEG C；Drying temperature is 20~100 DEG C.
In the sol-gel method, maturing temperature is 500~1000 DEG C.Preferably, the sol-gel method
In, the temperature of roasting is 600~700 DEG C.More preferably, the temperature of roasting is 700 DEG C in the sol-gel method
The sol-gel method is prepared in catalyst process, under the preferable temperature, drying time is preferably 2~
24 hours；Calcining time is preferably 2~6 hours.
In the precipitation method, M presoma, Cr presoma are first dispersed in aqueous solution and obtain mixed aqueous solution, wherein is mixed
M presoma, Cr precursor concentration in Heshui solution have a certain impact to the catalytic performance tool of the catalyst of preparation.The present invention
People has found, in the precipitation method, in the mixed aqueous solution, the concentration of chromium is 0.1~1mol/L.In the concentration of the chromium of the starting
Under, the variation of the specific surface of the catalyst of preparation is unobvious, and preparation section is high-efficient, and the catalytic performance of catalyst obtained has
It is promoted.The molar concentration of M and according to the M/Cr molar ratio of the catalyst convert.For example, the molar ratio of M and Cr is 1: 1
~1: 4；Preferably 1: 2~1: 3.
In the precipitation method, the lye is selected from least one aqueous solution of alkali metal hydroxide；Or ammonium hydroxide
And its water diluent.
Preferably, the lye is selected from the aqueous solution of at least one of ammonium hydroxide, sodium hydroxide, potassium hydroxide.
During precipitation reaction, the pH of system is controlled between 7~8.
In the precipitation method, the temperature of precipitation reaction is 50~90 DEG C, and drying temperature is 20~100 DEG C.
In the precipitation method, maturing temperature is 500~1000 DEG C.
Preferably, the temperature of roasting is 600~700 DEG C in the precipitation method；More preferably, the temperature of roasting is
700℃。
The precipitation method are prepared in catalyst process, and under the preferable temperature, drying time is preferably 2~24 small
When；Calcining time preferably 2~6 hours.
Catalyst provided by the present invention applies also for HCl tail gas in addition to it can be used to be catalyzed HCl oxidation and prepare chlorine
Catalytic treatment field.
The inventors discovered that the sol-gal process of use is the dispersed more excellent of the catalyst being prepared, it is obtained to urge
The stability of agent and the catalytic activity of HCl are better than other existing conventional methods, such as solid phase roasting method.
In addition, the present inventors have additionally discovered that, the CoCr that the catalyst used is prepared for sol-gel method2O4, preferred at this
Under catalyst, 430 DEG C of preferred catalytic reaction temperature, the raw materials components mole ratio 1: 1 of oxygen and hydrogen chloride.Under the optimum condition,
The stability of catalyst is high, and the catalytic oxidation activity of HCl is stronger.
Compared with existing copper system, aluminium chromium-based catalysts, the main active of catalyst is chromate MCr2O4(M=
Co, Zn) one or more of mixture, by XRD spectrum it can be seen that chromate is spinel-type, technical advantage exists
In: (1) higher low-temperature catalytic activity (such as catalytic reaction temperature is 360~400 DEG C, HCl conversion ratio can maintain 81~
90%)；(2) higher stability under reaction condition；(3) nontoxic；(4) (reaction temperature may be up to 500 DEG C of condition to high temperature resistant
Under, catalyst activity also has no inactivation).
Detailed description of the invention
Fig. 1 is the XRD spectrum that product is made in each embodiment or comparative example, wherein (a) CoCr2O4(embodiment 1), (b)
ZnCr2O4(embodiment 2), (c) Cr2O3(comparative example 3), (d) Cr2O3/Al2O3(comparative example 1)
Fig. 2 is the SEM photograph of catalyst made from embodiment 1-2, wherein Fig. 2 (a) is CoCr made from embodiment 12O4
SEM figure, Fig. 2 (b) be embodiment 2 made from ZnCr2O4SEM figure；
Fig. 3 is XPS map (a) CoCr of the Cr element of product made from each embodiment or comparative example2O4(embodiment 1),
(b)ZnCr2O4(embodiment 2), (c) Cr2O3(comparative example 3), (d) Cr2O3/Al2O3(comparative example 1)；
Fig. 4 is influence of the product made from each embodiment or comparative example to hydrogen chloride conversion ratio (in reaction 10 hours)；Its
In CoCr2O4For product made from embodiment 1；CoCr2O4(embodiment 1), ZnCr2O4(embodiment 2), Cr2O3(comparative example 3),
Cr2O3/Al2O3(comparative example 1)
Fig. 5 is 100 hours stability results of cobalt-chromate, chromic acid zinc catalyst；
Fig. 6 is influence of the reaction temperature to cobalt-chromate catalyst activity；
Fig. 7 is the influence that hydrogen chloride and oxygen feeding compare cobalt-chromate catalyst activity.
Specific embodiment:
[embodiment 1] sol-gel method cobalt-chromate (CoCr2O4) catalyst (cobalt chromium molar ratio 1: 2)
(a) by the cabaltous nitrate hexahydrate of 1.82g, 5.0 gram of nine water chromic nitrate, the Citric Acid Mono of 4.0g, addition 25mL water
Distilled water wiring solution-forming (starting aqueous solution)；
(b) solution that (a) is obtained water-bath heating stirring at 80 DEG C is added 2~3g of dispersing agent polyethylene glycol (400),
When moisture soon evaporates dry doubling into sticky gel, it is put at 80 DEG C and dries 2h, and through 700 DEG C of calcining (roasting) 2h；
(c) catalyst calcined is taken out, takes the catalyst of 40~60 mesh to carry out chlorination hydrogen catalysis after mortar grinder anti-
It answers.
Through XRD diagram spectrum analysis, CoCr made from the present embodiment2O4XRD spectrum see (a) spectral line of Fig. 1, with standard
CoCr2O4Map (JCPDS 22-1084) coincide.
CoCr made from the present embodiment2O4SEM see part (a) of Fig. 2.
CoCr made from the present embodiment2O4XPS see (a) spectral line of Fig. 3.
Obtain through elemental analysis: cobalt accounts for the 26.4% of catalyst weight in catalyst, and chromium accounts for the 46.4% of catalyst weight,
Cobalt-chromate accounts for catalyst content 99.4%.Specific surface area of catalyst is 29.5m2It is 18nm that/g, XRD, which calculate crystal particle diameter size,.
[embodiment 2] sol-gel method zinc chromate (ZnCr2O4) catalyst (zinc chrome molar ratio 1: 2)
(a) by the zinc nitrate hexahydrate of 1.86g, 5.0 gram of nine water chromic nitrate, the Citric Acid Mono of 4.0g is added to 25mL
Distilled water wiring solution-forming；
(b) solution that (a) is obtained water-bath heating stirring at 80 DEG C is added 2~3g of dispersing agent polyethylene glycol (400),
When moisture soon evaporates dry doubling into sticky gel, it is put at 80 DEG C and dries 2h, and through 700 DEG C of calcining (roasting) 2h；
(c) catalyst calcined is taken out, takes the catalyst of 40~60 mesh to carry out chlorination hydrogen catalysis after mortar grinder anti-
It answers.
Through XRD diagram spectrum analysis, ZnCr made from the present embodiment2O4XRD spectrum see (b) spectral line of Fig. 1, with standard
ZnCr2O4Map (JCPDS 22-1107) coincide.
ZnCr made from the present embodiment2O4SEM see part (b) of Fig. 2.
ZnCr made from the present embodiment2O4XPS see (b) spectral line of Fig. 3.
Obtain through elemental analysis: zinc accounts for the 25.3% of catalyst weight in catalyst, and chromium accounts for the 45.7% of catalyst weight,
Zinc chromate accounts for catalyst content 94.6%.Specific surface area of catalyst is 24.6m2It is 27nm that/g, XRD, which calculate crystal particle diameter size,.
[embodiment 3] precipitation method cobalt-chromate (CoCr2O4) catalyst (cobalt chromium molar ratio 1: 2)
(a) by the cabaltous nitrate hexahydrate of 1.82g, 5.0 gram of nine water chromic nitrate is added to the distilled water wiring solution-forming of 25mL
(mixed aqueous solution)；
(b) then the solution that (a) is obtained heating water bath at 80 DEG C is added ammonium hydroxide adjusting and arrives pH=7 or so, has a large amount of
Precipitating generate.Stop stirring and continue heating water bath, ageing a period of time allows the precipitating of generation constantly to grow up.Pass through filtration washing
Afterwards, it is put at 80 DEG C and dries 2h, and through 700 DEG C of calcining (roasting) 2h；
(c) catalyst calcined is taken out, 40~60 catalyst is taken to carry out the reaction of chlorination hydrogen catalysis after mortar grinder.
Obtain through elemental analysis: cobalt accounts for the 25.8% of catalyst weight in catalyst, and chromium accounts for the 44.2% of catalyst weight,
Cobalt-chromate accounts for catalyst content 90.4%, specific surface area of catalyst 19.6m2/ g, calculating crystal particle diameter size through XRD is
47nm。
[embodiment 4] sol-gel method cobalt-chromate (CoCr2O4) catalyst (cobalt chromium molar ratio 1: 1)
(a) by the cabaltous nitrate hexahydrate of 3.64g, 5.0 gram of nine water chromic nitrate, the Citric Acid Mono of 4.0g is added 25mL's
Distilled water wiring solution-forming；
(b) solution that (a) is obtained water-bath heating stirring at 80 DEG C is added 2~3g of dispersing agent polyethylene glycol (400),
When moisture soon evaporates dry doubling into sticky gel, it is put at 80 DEG C and dries 2h, and through 700 DEG C of calcining (roasting) 2h；
(c) catalyst calcined is taken out, takes the catalyst of 40~60 mesh to carry out chlorination hydrogen catalysis after mortar grinder anti-
It answers.
Obtain through elemental analysis: obtaining through elemental analysis: cobalt accounts for the 38.4% of catalyst weight, chromium Zhan Cuihua in catalyst
The 32.4% of agent weight, cobalt-chromate account for catalyst content 75%, specific surface area of catalyst 24.3m2/g。
[embodiment 5] sol-gel method cobalt-chromate (CoCr204) catalyst (cobalt chromium molar ratio 1: 2 is compared with embodiment 1,
The inventory of Citric Acid Mono influences (additional amount of Citric Acid Mono is reduced to half))
(a) by the cabaltous nitrate hexahydrate of 1.82g, 5.0 gram of nine water chromic nitrate, the Citric Acid Mono of 2.0g is added 25mL's
Distilled water wiring solution-forming；
(b) solution that (a) is obtained water-bath heating stirring at 80 DEG C is added 2~3g of dispersing agent polyethylene glycol (400),
When moisture soon evaporates dry doubling into sticky gel, it is put at 80 DEG C and dries 2h, and through 700 DEG C of calcining (roasting) 2h；
(c) catalyst calcined is taken out, takes the catalyst of 40~60 mesh to carry out chlorination hydrogen catalysis after mortar grinder anti-
It answers.
Obtain through elemental analysis: cobalt accounts for the 26.2% of catalyst weight in catalyst, and chromium accounts for the 46.7% of catalyst weight,
Cobalt-chromate accounts for catalyst content 92.4%.Specific surface area of catalyst is 25.1m2/g。
[embodiment 6] sol-gel method cobalt-chromate (CoCr2O4) catalyst (cobalt chromium molar ratio 1: 2 is compared with embodiment 1,
Calcination temperature is increased to 900 DEG C)
(a) by the cabaltous nitrate hexahydrate of 1.82g, 5.0 gram of nine water chromic nitrate, the Citric Acid Mono of 4.0g is added 25mL's
Distilled water wiring solution-forming；
(b) solution that (a) is obtained water-bath heating stirring at 80 DEG C is added 2~3g of dispersing agent polyethylene glycol (400),
When moisture soon evaporates dry doubling into sticky gel, it is put at 80 DEG C and dries 2h, and through 900 DEG C of calcining (roasting) 2h；
(c) catalyst calcined is taken out, takes the catalyst of 40~60 mesh to carry out chlorination hydrogen catalysis after mortar grinder anti-
It answers.
Obtain through elemental analysis: cobalt accounts for the 26.7% of catalyst weight in catalyst, and chromium accounts for the 46.3% of catalyst weight,
Cobalt-chromate accounts for catalyst content 99.2%.Specific surface area of catalyst is 18.2m2/g。
[comparative example 1] chromium oxide/activated alumina impregnation catalyst agent
(a) by the Chromium nitrate (Cr(NO3)3),nonahydrate of 5.0g, it is added to wiring solution-forming in the distilled water of 25mL, is added in Xiang Suoshu solution
40~60 mesh activity Al2O3Carrier simultaneously impregnates 12 hours；
(b) it filters off the solution and obtains impregnated carrier, 2h is dried at 80 DEG C, and through 700 DEG C of calcining 2h.Had
There is the catalyst of catalytic activity.
Chromium oxide/activated alumina XRD spectrum made from this comparative example is shown in (d) spectral line of Fig. 1.
Chromium oxide/activated alumina XPS made from this comparative example is shown in (d) spectral line of Fig. 3.
Obtain through elemental analysis: chromium accounts for the 7.5% of catalyst weight in catalyst.Specific surface area of catalyst is 205.4m2/
g。
[comparative example 2] chromium oxide/titanic oxide impregnation catalyst
(a) by the Chromium nitrate (Cr(NO3)3),nonahydrate of 5.0g, wiring solution-forming in the distilled water of 25mL is added, is added 40 in Xiang Suoshu solution
~60 mesh activity TiO2Carrier simultaneously impregnates 12 hours；
(b) it filters off the solution and obtains impregnated carrier, 2h is dried at 80 DEG C, and through 700 DEG C of calcining 2h.Had
There is the catalyst of catalytic activity.
Obtain through elemental analysis: chromium accounts for the 8.3% of catalyst weight, specific surface area of catalyst 155.3m in catalyst2/
g。
[comparative example 3] sol-gel method chromium oxide catalyst
(a) by 5.0 gram of nine water chromic nitrate, the distilled water wiring solution-forming of 25mL is added in the Citric Acid Mono of 4.0g；
(b) solution at 80 DEG C water-bath heating stirring, be added 2~3g of dispersing agent polyethylene glycol (400), when moisture soon
Evaporation dry doubling is put at 80 DEG C at sticky gel and dries 2h, and through 700 DEG C of calcining 2h；
(c) catalyst calcined is taken out, 40~60 catalyst is taken to carry out the reaction of chlorination hydrogen catalysis after mortar grinder.
The XRD spectrum of chromium oxide made from this comparative example is shown in (c) spectral line of Fig. 1.
The XPS of chromium oxide made from this comparative example is shown in (c) spectral line of Fig. 3.
Obtain through elemental analysis: chromium accounts for catalyst weight content 67% in catalyst.Specific surface area of catalyst is 13.7m2/
g。
[embodiment 7] catalyst performance evaluation
Comparative catalyst made from catalyst and comparative example 1-3 to above-described embodiment 1~6 in fixed bed reactors into
The performance evaluation of row catalytic oxidation of hydrogen chloride for preparing chlorine gas.0.7g catalyst is added in reaction tube, with 5 DEG C/min of heating rate
430 DEG C are heated to from room temperature, is passed through the mixed gas of hydrogen chloride and oxygen, hydrogen chloride flow is 10mL/min, and oxygen flow is
It when 10mL/min, carrier gas nitrogen flow 150mL/min, reacts 2 hours, absorbs 3 points with the KI solution that 100mL concentration is 10%
Clock, with calibrated Na2S2O3The Cl that solution titration generates2.The conversion ratio of HCl is calculated, and when with unit mass catalyst unit
Activity of the amount of chlorine of interior generation as catalyst.
The performance comparison result of catalyst prepared by the present invention is as shown in table 1 and Fig. 4.
1 catalyst catalytic oxidation of hydrogen chloride for preparing chlorine gas performance of table compares
Comparative example 4*For the data of patent EP0184413 embodiment 1, comparative example 5**For patent US5707919 embodiment 3
Data, comparative example 6***For the data of patent CN104785271A embodiment 1.
It can be seen that the good activity of (1) Examples 1 to 2 performance and stability from table 1, Fig. 4.Its activity is higher than other
The data of several related patents reports.(2) comparative example 1 is begun to decline after stabilizing 4 hours, illustrates three oxidations two of support type
Active force between chromium and carrier is inadequate, so that chrome green starts to be lost after a period of time.(3) comparative example 3, pure
Cr 2 O 3 catalyst stability and activity are all very low, coincide with document report.(4) optimal catalyst is the chromium of embodiment 1
Sour Co catalysts.
[embodiment 8] CoCr2O4And ZnCr2O4Catalytic stability test
With catalyst CoCr in embodiment 12O4With the ZnCr with embodiment 22O4For, research spinel-type catalyst
Catalytic stability.Test condition is described in embodiment 7, and test result is shown in Fig. 5.As described in Figure 5, from top to bottom it is respectively
CoCr2O4、ZnCr2O4Measurement result.(experiment condition is equal to embodiment 7: catalyst 0.7g, embodiment 1 and embodiment 2
Catalyst, reaction temperature be 430 DEG C, HCl=10mL/min, O2=10mL/min, N2=150mL/min.)
As seen from Figure 5, (1) cobalt-chromate, the stability of zinc chromate and catalytic activity are all very high.(2) reaction 100 is small
Shi Hou, the activity of cobalt-chromate have dropped 2%, and the activity of zinc chromate has dropped 5%, illustrate that cobalt-chromate stability is more preferable.
[embodiment 9] reaction temperature influences catalytic activity
With catalyst CoCr in embodiment 12O4For, spinel-type catalyst is studied under different reaction temperatures, chlorination
The variation of the conversion ratio of hydrogen.Test condition is referring to embodiment 7, only reaction temperature DEG C variation from 320 DEG C to 500.Test result exists
It is shown in Fig. 6.(experiment condition: catalyst 0.7g, 1 catalyst of embodiment, HCl=10mL/min, O2=10mL/min, N2=
150mL/min.Change reaction temperature T=320~500 DEG C.)
As seen from Figure 6, when temperature is at 320 DEG C, reactivity is also relatively low, and only 45%；But work as temperature liter
When height is to 360 DEG C, conversion ratio is increased to rapidly 81%；As temperature continues to rise, conversion ratio slowly rises, and reaches at 430 DEG C
Maximum 93%, close to reaction balance.It is therefore seen that working as 360~400 DEG C of reaction temperature, catalyst can have 81~93% chlorine
Change hydrogen conversion ratio.This performance is higher than synthermal lower performance reported in document.It is preferable to illustrate that the catalyst of this patent has
Low temperature active.When temperature continues to increase, conversion ratio is begun to decline.This is because this reaction is exothermic reaction, temperature is higher anti-
It should start to be moved to the left.
[embodiment 10] hydrogen chloride and oxygen proportion are to CoCr2O4Catalytic activity influences
With catalyst CoCr in embodiment 12O4For, spinel-type catalyst is studied under different charge ratios, hydrogen chloride
Conversion ratio variation.Test condition is embodiment 7, and difference is that charge ratio changes HCl/O2=4~0.5.(experiment condition:
Catalyst is 0.7g, and 1 catalyst of embodiment, reaction temperature is 430 DEG C, HCl=10mL/min, N2=150mL/min.Change oxygen
The flow of gas is respectively 2.5mL/min, 5mL/min, 10mL/min, 20mL/min.) test result shows in Fig. 7.
As seen from Figure 7, when the raw materials components mole ratio of hydrogen chloride and oxygen is 4: 1, conversion ratio is less than 50%；Work as chlorination
When the raw materials components mole ratio of hydrogen and oxygen is 2: 1, conversion ratio is increased to rapidly 84%；When the raw materials components mole ratio of hydrogen chloride and oxygen is
When 1: 1, conversion ratio reaches maximum 93%；When the flow-rate ratio of hydrogen chloride and oxygen continues to increase, conversion ratio is not further added by.
Claims (6)
1. a kind of method of preparing chlorine by catalytic oxidation of hydrogen chloride, which is characterized in that oxygen, hydrogen chloride are contacted with catalyst,
The molar ratio for controlling hydrogen chloride and oxygen is 4:1~1:4, and reaction temperature is 400~450 DEG C, carries out catalytic oxidation and is made
Chlorine；
The catalyst is made using sol-gel method, preparation step are as follows:
In M and Cr molar ratio 1:2 ~ 1:3 ratio by M presoma, Cr presoma, citric acid be dispersed in water starting it is water-soluble
Liquid；It is then mixed again with water soluble polymer, hydro-thermal reaction forms gel, then roasts, grinds through drying, 600~700 DEG C
The catalyst is made in mill, sieving；In the starting aqueous solution, the concentration of citric acid is the moL/L of 0.1 moL/L ~ 1；
Wherein, M presoma is at least one of water-soluble cobalt compound, zinc compound；Cr presoma is the water solubility of chromium
Compound；
In the catalyst comprising chemical formula be MCr2O4Chromate at least one, wherein M be selected from Co or Zn；Described
Chromate has spinel structure, and crystal particle diameter size is 15 ~ 30nm；The specific surface area of catalyst is 25~30m2/g。
2. the method as described in claim 1, which is characterized in that in the starting aqueous solution, the molar concentration of Cr is 0.1~
1moL/L。
3. the method as described in claim 1, which is characterized in that the water soluble polymer is polyethylene glycol, gathers
At least one of vinyl alcohol or polyvinylpyrrolidone.
4. the method as described in claim 1, which is characterized in that the dosage of the water soluble polymer is Cr forerunner
0.4 ~ 0.8 times of weight.
5. method as claimed in claim 3, which is characterized in that polyethylene glycol adds in form of an aqueous solutions, mass concentration
It is 5% ~ 15%.
6. the method as described in claim 1, which is characterized in that the molar ratio of hydrogen chloride and oxygen is 0.5~1；Reaction temperature
It is 400~450 DEG C.
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Citations (2)
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|---|---|---|---|---|
| CN85109387A (en) * | 1984-12-03 | 1986-06-10 | 三井东压化学有限公司 | Production process of chlorine |
| CN1713956A (en) * | 2002-08-22 | 2005-12-28 | 纳幕尔杜邦公司 | Cobalt-substituted chromium oxide compositions, their preparation, and their use as catalysts and catalyst precursors |
-
2016
- 2016-07-15 CN CN201610556565.7A patent/CN106560239B/en active Active
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85109387A (en) * | 1984-12-03 | 1986-06-10 | 三井东压化学有限公司 | Production process of chlorine |
| CN1713956A (en) * | 2002-08-22 | 2005-12-28 | 纳幕尔杜邦公司 | Cobalt-substituted chromium oxide compositions, their preparation, and their use as catalysts and catalyst precursors |
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| Title |
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| S.A.Hosseini et al.MCr2O4 (M¼Co, Cu,andZn)nanospinelsfor2-propanol.《Ceramics International》.2013,第39卷9253-9261. |
| The effect of microstructural properties of CoCr2O4spinel oxides oncatalytic combustion of dichloromethane;Jing-Di Liu et al;《Applied Surface Science》;20160206;第369卷;58-66 |
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