CN109675582A - A kind of preparing chlorine by oxidizing hydrogen chloride catalyst and preparation method thereof - Google Patents
A kind of preparing chlorine by oxidizing hydrogen chloride catalyst and preparation method thereof Download PDFInfo
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- CN109675582A CN109675582A CN201811588792.3A CN201811588792A CN109675582A CN 109675582 A CN109675582 A CN 109675582A CN 201811588792 A CN201811588792 A CN 201811588792A CN 109675582 A CN109675582 A CN 109675582A
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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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8926—Copper and noble metals
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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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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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
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/462—Ruthenium
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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
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/652—Chromium, molybdenum or tungsten
- B01J23/6522—Chromium
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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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- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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Abstract
The invention discloses a kind of preparing chlorine by oxidizing hydrogen chloride catalyst and preparation method thereof.Preparing chlorine by oxidizing hydrogen chloride catalyst of the present invention roasts the percentage composition of forerunner's weight are as follows: component A:80%~82%；Component B:8%~10%；Component C:8%；Component D:2%.Wherein component A is gama-alumina, and component B is copper Cu2+, chromium Cr3+, ruthenium Ru3+One of or it is a variety of, component C be zirconium oxychloride, component D be silica.The catalyst preparation step includes: firstly, preparing the aqueous solution of one of copper, chromium, ruthenium or a variety of nitrate or chloride；Gama-alumina powder is added, is adjusted to neutrality with ammonium hydroxide；Zirconium oxychloride is added in above-mentioned solution, heating stirring reflux, then is adjusted to alkalescent with ammonium hydroxide and filters, dried；Finally, mixing and forming solid material with silica, 500 DEG C of calcination process obtain heavy oil hydrogenating treatment catalyst.The catalyst is mainly used in hydrogen chloride and Oxygen Catalytic Oxidation prepares the reaction process of chlorine.
Description
Technical field
The invention belongs to catalytic fields, and in particular to the long-life chloration hydro-oxidation that a kind of inactive component is lost prepares chlorine
Catalyst of gas and preparation method thereof.
Background technique
Chlorine is a kind of important Elementary Chemical Industry raw material, be widely used in polyurethane, organosilicon, chlorinated hydrocabon, epoxy resin,
The fields such as chlorinated rubber, chlorinated high polymers.
If the hydrogen chloride of by-product can be directly prepared into chlorine, the closed loop circulation of " chlorine " can be realized as, thus
In two bottlenecks of upstream and downstream for fundamentally solving consumption chlorine industry.Chlorine is manufactured using oxygen or air as oxidation oxidation chlorination hydrogen,
It is one
Good approach.Its stoichiometric equation can indicate are as follows:
The industrial process that can be realized the process at present has three classes, is catalytic oxidation, cyclic oxidation and oxygen respectively
Change electrolysis method.Wherein the Typical Representative of cyclic oxidation is E.I.Du Pont Company, which uses sulfuric acid to make as the oxide isolation of circulation
It is catalyst with nitric acid, therefore equipment throwing foot is very big, complicated for operation, operating cost is high, flexibility is poor.Oxidization electrolysis method can
Alleviate the unbalanced problem of chlor-alkali in current chlor-alkali industry well, but its power consumption is still above 1700kWh/ tons, not
Have in the high power consumption for fundamentally solving the problems, such as chlorine production, and for the electrolysis of relative ion film, the method for oxidization electrolysis hydrochloric acid
Equipment it is more complicated, economy and operability are without advantage.The technology only has Beyer Co., Ltd at present and grasps, but itself
The more positive catalytic oxidation technologies for promoting the technology and Introduced from Japan Sumitomo outward.
Although the equipment investment of the catalytic oxidation of hydrogen chloride technology is also bigger, maximum advantage is that power consumption is low,
And it is an environmentally protective chemical process, and heavy oil hydrogenating treatment catalyst is the core technology of catalytic oxidation.
In reported heavy oil hydrogenating treatment catalyst, active component mainly uses the metals such as copper, chromium, ruthenium, and these types is living
Property component is more in the catalyst exists in the form of an oxide.The catalyst that Sumitomo Chemical Co uses ruthenium compound to prepare
(CN1475434A) there is good reactivity worth, but for a long time after reaction, there are loss of active component and reaction to live for catalyst
Property decline the problem of.During the reaction, active component is in miscellaneous in Strong oxdiative state Shi Keyu hydrogen chloride or reaction system
Matter (such as sulphur) chemically reacts, and the metal chloride of formation is dissolved in water in reaction mass, so as to cause active group shunting
It loses；Since the reaction mostly carries out at high temperature, there is direct gasification loss in catalyst activity component at high temperature
(CN87104744A, CN1475434A, CN101125297A, CN202236397A, CN102000583A), so as to cause catalysis
The decline of agent activity, catalytic life shorten.
Summary of the invention
The technical problem to be solved by the present invention is to overcome the shortcomings of above-mentioned background technique, a kind of inactive component stream is provided
Long-life heavy oil hydrogenating treatment catalyst of mistake and preparation method thereof.The catalyst is mainly used in hydrogen chloride and Oxygen Catalytic Oxidation
Prepare the reaction process of chlorine.
Major technique design of the invention is as follows:
Hydrolysis can occur under weak basic condition and generate zirconium hydroxide for zirconium oxychloride, and being formed after high-temperature roasting has weak acid
The zirconium oxide of property.Easily with catalytic active components such as copper, chromium, rutheniums strong interaction occurs for the compound at high temperature, and aoxidizes
Zirconium chemical property is stablized, and not easily runs off in hydrogen chloride oxidation reaction environment, therefore the present invention uses zirconium oxide to active component
Cladding processing is carried out, not only the modulation acid-base property of catalyst, but also significantly reduced because that chemistry occurs is anti-for active component and hydrogen chloride
Metal loss caused by answering, to significantly enhance catalytic reaction activity and its stability.
Preparing chlorine by oxidizing hydrogen chloride catalyst of the present invention, it is characterised in that catalyst roasts forerunner's weight percentage
Composition are as follows:
Component A:80%~82%；
Component B:8%~10%；
Component C:8%；
Component D:2%.
Wherein component A is gama-alumina, and component B is copper Cu2+, chromium Cr3+, ruthenium Ru3+One of or it is a variety of, component C is
Zirconium oxychloride, component D are silica.
Preparing chlorine by oxidizing hydrogen chloride catalyst of the invention is prepared by the following method:
A) contain copper, chromium, one of ruthenium or a variety of nitrate or chloride is configured to concentration as the water-soluble of 1mol/L
Liquid；
B) according to component A and component B mass ratio 8-10:1, it is resulting that step a is added in the gama-alumina powder after drying
In aqueous solution, it is adjusted to neutrality under stirring condition with ammonium hydroxide；
C) it is 1:10 according to component C and component A mass ratio, zirconium oxychloride is added in the resulting solution of step b, heating is stirred
Reflux 8h is mixed, then is adjusted to alkalescent with ammonium hydroxide, continues to stir 2h, filter, wash, drying；
D) the resulting solid material of step c is uniformly mixed with silica, is granulated, and compression moulding, the catalyst precursor exists
Under the conditions of 500 DEG C of temperature, calcination process 12h obtains preparing chlorine by oxidizing hydrogen chloride catalyst.
The invention has the following advantages that
Preparing chlorine by oxidizing hydrogen chloride catalyst of the invention, catalyst activity component are not lost, long catalytic life.It is reacting
After 1000h, catalyst activity component turnover rate is lower than 0.5%, and reactivity is without being decreased obviously, and catalytic life is compared to existing skill
(referring to the catalyst of CN1475434A preparation, after reacting 1000h, catalyst activity component turnover rate is 7.6% to art, and reaction is lived
Property compared to initial reaction stage decline 23%) significantly improve.
Specific embodiment
In the present invention, preparing chlorine by oxidizing hydrogen chloride catalyst activity evaluating apparatus is common fixed-bed tube reactor, instead
Answer device having a size ofIt is by particleCatalyst packing into reactor, add
Heat to reaction temperature, gas stablizes sampling analysis after reaction by pressure reducing valve and flowmeter rear feeding.
Catalyst activity evaluation experimental condition: 300-400 DEG C of reaction temperature, molar ratio/volume ratio of hydrogen chloride and oxygen
For 1:(0.5~3), reaction pressure normal pressure or micro-positive pressure.
Oxidation reactor outlet is mainly the mixture of chlorine, oxygen, hydrogen chloride and water vapour, analyzes chlorine therein and contains
Measure and calculate the production quantity of chlorine in certain time interval, so that it may the conversion ratio of oxidation reaction is calculated, to investigate catalyst
The affecting laws of activity and oxidation reaction condition.
According to the principle that chlorine is easily absorbed by liquor kalii iodide, the reproducibility of iodide ion is utilized in other words, and measurement has oxygen
The amount of the chlorine for the property changed.When gas sample is passed through liquor kalii iodide, chlorine is absorbed, and displaces iodine, and the iodine of precipitation is used thio again
The titration of sulfuric acid sodium standard solution, this is iodimetric titration (or indirect iodometric processes, iodometry).
Titration process is using starch as indicator.Since HCl is highly soluble in water, so in Cl2It is absorbed by KI solution
Meanwhile HCl is also absorbed simultaneously.After being titrated with hypo solution, it can titrate HCl's with standard solution of sodium hydroxide
Amount, the titrimetry phenolphthalein indicator.
Specific steps are as follows: preparing the KI solution of portion 20% at regular intervals after system stable operation
100ml, switching oxidation reactor export triple valve, mixed gas after reaction are passed into (100ml) liquor kalii iodide of constant volume
In, it absorbs 3 minutes, moves into absorbing liquid in conical flask after absorption, titrated with the sodium thiosulfate standard solution of 0.1mol/l, with
Starch makees indicator；Followed by, with phenolphthalein indicator, titrated with 0.1mol/l standard solution of sodium hydroxide unreacted
HC1。
HCl conversion ratio:
Conv%=b/ (b+d) * 100%
B indicates that titration consumes Na2S2O3Solution ml, ml
D indicates that titration consumes NaOH solution ml, ml
The catalyst sample of differential responses time is subjected to X-fluorescence elemental analysis, catalyst uses active component after 1000h
Turnover rate calculation method is as follows:
Loss of active component rate=(catalyst uses rear active component content using preceding active component content-catalyst)/
Catalyst uses preceding active component content
The present invention is described in further details below with reference to embodiment.
Embodiment 1
Preparing chlorine by oxidizing hydrogen chloride catalyst of the invention roasts the percentage composition of forerunner's weight are as follows:
Component A:80%；
Component B:10%；
Component C:8%；
Component D:2%.
Wherein component A is gama-alumina, and component B is copper nitrate and ruthenic chloride, and component C is zirconium oxychloride, and component D is oxygen
SiClx.
Preparing chlorine by oxidizing hydrogen chloride catalyst of the invention is prepared by the following method:
It a) is aqueous solution that 1:2 is configured to that concentration is 1mol/L by copper nitrate and ruthenic chloride mass ratio；
It b) is 8:1 according to component A and component B mass ratio, it is resulting that step a is added in the gama-alumina powder after drying
In aqueous solution, it is adjusted to neutrality under stirring condition with ammonium hydroxide；
C) it is 1:10 according to component C and component A mass ratio, zirconium oxychloride is added in the resulting solution of step b, heating is stirred
Reflux 8h is mixed, then is adjusted to alkalescent with ammonium hydroxide, continues to stir 2h, filter, wash, drying；
D) the resulting solid material of step c is uniformly mixed with silica, is granulated, and compression moulding, the catalyst precursor exists
Under the conditions of 500 DEG C of temperature, calcination process 12h obtains preparing chlorine by oxidizing hydrogen chloride catalyst, is labeled as A.
Embodiment 2
Preparing chlorine by oxidizing hydrogen chloride catalyst of the invention roasts the percentage composition of forerunner's weight are as follows:
Component A:82%；
Component B:8%；
Component C:8%；
Component D:2%.
Wherein component A is gama-alumina, and component B is chromic nitrate and ruthenic chloride, and component C is zirconium oxychloride, and component D is oxygen
SiClx.
Preparing chlorine by oxidizing hydrogen chloride catalyst preparation of the invention with embodiment 1, except that the chromic nitrate of step a and
Aluminium chloride mass ratio is 1:1, and component A and component B the mass ratio 10:1 of step b obtains preparing chlorine by oxidizing hydrogen chloride catalyst, is marked
It is denoted as B.
Embodiment 3
Preparing chlorine by oxidizing hydrogen chloride catalyst of the invention roasts the percentage composition of forerunner's weight are as follows:
Component A:82%；
Component B:9%；
Component C:8%；
Component D:2%.
Wherein component A is gama-alumina, and component B is ruthenic chloride, and component C is zirconium oxychloride, and component D is silica.
Preparing chlorine by oxidizing hydrogen chloride catalyst preparation of the invention is with embodiment 1, except that step a is ruthenic chloride
Solution, component A and component B the mass ratio 9:1 of step b, obtains preparing chlorine by oxidizing hydrogen chloride catalyst, is labeled as C.
The application of heavy oil hydrogenating treatment catalyst of the invention:
Preparing chlorine by oxidizing hydrogen chloride catalyst A, B, C prepared by Examples 1 to 3 are loaded into fixed bed pipe reaction
Device, loaded catalyst 30mL, 360 DEG C of reaction temperature, molar ratio/volume ratio of hydrogen chloride and oxygen is 1:2, reaction pressure
Normal pressure, hydrogen chloride feed rate are 100mL/min.Stablize reaction for 24 hours with sampling analysis after reaction 1000h, calculates conversion ratio.It will
X-fluorescence elemental analysis is carried out using the catalyst sample after preceding and reaction 1000h, calculates loss of active component based on the analysis results
Rate.As a result as shown in the table:
1 preparing chlorine by oxidizing hydrogen chloride Catalyst Conversion of table
Claims (2)
1. a kind of preparing chlorine by oxidizing hydrogen chloride catalyst, it is characterised in that catalyst roasts the percentage composition of forerunner's weight are as follows:
Component A:80%~82%；
Component B:8%~10%；
Component C:8%；
Component D:2%.
Wherein component A is gama-alumina, and component B is copper Cu2+, chromium Cr3+, ruthenium Ru3+One of or it is a variety of, component C be oxygen chlorine
Change zirconium, component D is silica.
2. a kind of preparation method of preparing chlorine by oxidizing hydrogen chloride catalyst as described in claim 1, it is characterised in that including with
Lower step:
A) nitrate or chloride containing component B are configured to the aqueous solution that concentration is 1mol/L；
B) it is 8-10:1 according to the nitrate or chloride mass ratio of component A and component B, step a is added in the component A after drying
In resulting aqueous solution, it is adjusted to neutrality under stirring with ammonium hydroxide；
C) it is 1:10 according to component C and component A mass ratio, component C is added in the resulting solution of step b, heating stirring reflux
8h, then it is adjusted to alkalescent with ammonium hydroxide, continue to stir 2h, filter, wash, drying obtains solid material；
D) the resulting solid material of step c is uniformly mixed with component D, is granulated, compression moulding obtains catalyst precursor, in temperature
Calcination process 12h at 500 DEG C, obtains preparing chlorine by oxidizing hydrogen chloride catalyst.
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