CN104549360B - Catalyst for producing chlorine by catalytic oxidation of hydrogen chloride - Google Patents
Catalyst for producing chlorine by catalytic oxidation of hydrogen chloride Download PDFInfo
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- CN104549360B CN104549360B CN201410129773.XA CN201410129773A CN104549360B CN 104549360 B CN104549360 B CN 104549360B CN 201410129773 A CN201410129773 A CN 201410129773A CN 104549360 B CN104549360 B CN 104549360B
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Abstract
The invention relates to a catalyst for producing chlorine by catalytic oxidation of hydrogen chloride, and particularly relates to a catalyst which is prepared by a twice-impregnation method and contains ruthenium, copper, alkali metals and rare-earth metal elements. The catalyst has a core-shell structure.
Description
Technical field
The present invention relates to the catalyst used in a kind of hydrogen chloride production chlorine technique for catalysis oxidation, and in particular to one
The catalyst containing ruthenium, copper and alkali metal and thulium prepared by infusion process twice is planted, this is urged
Agent has core shell structure.
Background technology
In various industries such as metallurgy, weaving, medicine, chlor-alkali, petrochemical industry, with the amount of hydrogen chloride produced by by-product form
It is huge.Substantial amounts of hydrogen chloride how is processed, a problem demanding prompt solution is had become.Actual use industrial at present
Main treatment measures are the hydrochloric acid sales honest and clean at a low price with matter is made after water absorbing hydrogen chloride；Because hydrochloric acid is cheap and market needs
Finite capacity is sought, hydrogen chloride is made into hydrochloric acid actually has become a kind of burden rather than turning waste into wealth.Also some uses
Treatment measures be with being discharged in alkali and directly after hydrogen chloride；It is gradually improved however as environmentally friendly laws and regulations, various discharge sides
The environmental protection standard of formula is very strict.
Therefore, it is capable of being industrialized that the method that hydrogen chloride is made chlorine has been subjected to giving more sustained attention for relevant industries.Because
Byproduct hydrogen chloride is directly prepared into the method for chlorine, the closed cycle of chlorine element can not only be realized, moreover it is possible to realize course of reaction
Zero-emission.Up to the present, hydrogen chloride prepares the method for chlorine and can be largely classified into three classes：Electrolysis, direct oxidation method and
Catalytic oxidation.But, the energy resource consumption of electrolysis technique is too big, and ionic membrane is also required to often replacing, and cost is very high, often
4000 yuan of ton chlorine cost recovery ＞；The yield of direct oxidation method is low, can not industrialize；Compared with electrolysis, direct oxidation method,
The catalytic oxidation most industrialization potential that catalytic oxidation especially reacts via Deacon.
Deacon reaction be in the presence of a catalyst by chloration hydro-oxidation into chlorine reaction.Deacon reaction sides
Formula is：The performance of catalyst is very big to the influential effect that Deacon reacts.
Therefore, in order to realize the industrialization that Decon reacts, domestic and international researcher has done substantial amounts of research to look for suitable catalyst.
The catalyst that Deacon reacts used is classified with active component, mainly using metallic elements such as chromium, ruthenium, copper.Its
In, chromium-based catalysts environmental pollution is larger；Ruthenium catalyst is expensive；Cu-series catalyst only has relatively low work at low temperature
Property, but be easy to be lost at high temperature so that catalysis activity reduction.
Disclose the method with chromium oxide as catalyst oxidation chlorination hydrogen in EP0184413, but catalyst activity compared with
It is low；Because chromium easily forms lower boiling chromium oxychloride with chlorine, reaction temperature higher easily inactivates catalyst.
US5707919 discloses a kind of improved method of chromium oxide catalyst, and the catalyst activity prepared through the method is high, the life-span
Relatively long, hydrogen chloride conversion ratio is 85.2%.In addition, CN1126637A, CN85109387A, CN87105455A etc. are disclosed
Catalyst with chromium oxide as major constituent, but because chromium has larger toxicity, chromium oxide catalyst is dirty because there is serious environment
Dye problem, limits its application industrially.
GB2120225 uses coprecipitation to be prepared for the copper oxide catalyst with titanium dioxide as carrier, but in catalyst
The substantial amounts of waste water containing heavy metal ion is generated in preparation process.US4123389 is disclosed with silica gel, titanium oxide or aluminum oxide
It is the copper oxide catalyst of carrier；But because catalyst proofing process needs to carry out in organic solvent, to the pollution of environment compared with
For serious.It is catalyst that CN101125297A is disclosed to load copper chloride, potassium chloride and cerium chloride on the alumina support, so
The catalyst is processed with phosphoric acid afterwards；Due to the CuCl under higher reaction temperatures2Active component is easily lost in, and causes catalysis
The service life of agent is shorter.CN102658149A discloses CuO, K2The copper-based catalysts of O and carrier composition, but the catalyst pair
It is relatively low in the conversion ratio of hydrogen chloride, only up to 88.6%.CN102000583A is disclosed with copper as main active component, addition
The catalyst of the auxiliary agents such as boron, transition metal, rare earth element and alkali metal/alkaline-earth metal；But catalyst reaction 100h
Afterwards, chlorine yield is up to 89%, need further raising.
GB1046313 discloses one kind with silica gel, float stone and A12O3It is the support type RuCl of carrier3Catalyst, but this urges
Agent is easy to inactivation.US5908607A discloses one kind with RuO2It is the catalyst of major constituent, but the catalysis of the catalyst
Activity can gradually be reduced with the extension of the duration of runs, also easily because in the impurity and operational process of craft in chlorination hydrogen feedstock
Error causes the poisoning of irreversibility and inactivates.TW200812909A describes a kind of comprising tin ash and at least one containing ruthenium
The catalyst of compound.
Summary of the invention
In order to overcome the deficiencies in the prior art part, the present invention provides a kind of for catalysis oxidation hydrogen chloride production chlorine
Composite catalyst.
The present invention is related to a kind of catalyst for catalysis oxidation hydrogen chloride production chlorine in one aspect, contains ruthenium unit
Element, copper and alkali metal and thulium.
The present invention further relates to a kind of prepare catalyst for catalysis oxidation hydrogen chloride production chlorine in another aspect
Method, comprising：
A) by copper-containing compound, alkali metal-containing compound and it is dissolved in first liquid containing rare earth compound and is made first
Solution, to addition carrier and first impregnation in first solution；
B) filter off first solution and obtain the carrier that first impregnation is crossed, first drying simultaneously calcines the first impregnation for the first time
The carrier crossed is so as to obtain first burnt carrier；
C) it is dissolved in containing ruthenium compound and the second solution is made in second liquid, the addition first burnt carrier is simultaneously secondary
Dipping；
D) filter off second solution and obtain the carrier that double-steeping is crossed, dry again and calcine the double-steeping again
The carrier crossed is so as to obtain catalyst.
The present invention further relates to a kind of method of catalysis oxidation hydrogen chloride production chlorine in another aspect, including：
A) containing hydrogen chloride feed gas stream and the oxygenous logistics for aoxidizing the hydrogen chloride are supplied；
B) by the containing hydrogen chloride feed gas stream and for aoxidizing the oxygenous logistics of the hydrogen chloride with the present invention
The catalyst contact is reacted；
C) separated from the logistics reacted and obtain chlorine.
The present invention further relates to the catalyst for the purposes of catalysis oxidation hydrogen chloride production chlorine, bag in another aspect
Include：Containing hydrogen chloride feed gas stream and oxygenous logistics for aoxidizing the hydrogen chloride are connect with catalyst of the present invention
Touch and reacted.
Catalyst of the present invention have under low reaction temperatures keep high activity, change over time stability beneficial effect high
Really.
Detailed description of the invention
Inventor has found that the main of catalyst is disadvantageous in that in low reaction in prior art Deacon methods by research
At a temperature of activity it is relatively low and rise high reaction temperature then cause catalyst loss so that reduce reaction efficiency；Additionally, catalyst is at any time
Between change stability also have much room for improvement.Catalyst of the present invention significantly improves the activity of catalyst, can make the catalysis of each component
Ability is utilized, while eliminating catalyst loss caused by catalyst hot-spot, improves catalyst
Heat endurance during use.
The present invention is related to a kind of catalyst for catalysis oxidation hydrogen chloride production chlorine in one aspect, wherein containing
Ruthenium, copper, alkali metal and rare earth component, it is characterised in that：The content of copper accounts for 3.0~26.0wt% of catalyst weight；Alkali
The content of metal accounts for 0.2~4.0wt% of catalyst weight；The content of rare earth metal account for catalyst weight 0.2~
2.0wt%；The content of ruthenium accounts for 2.0~8.0wt% of catalyst weight.
The content of copper of the present invention can be any in arbitrary value or the scope in 3.0~26.0wt% scopes
Value combination formed scope, such as 3.0%, 3.5%, 4.0%, 4.5%, 5.0%, 5.5%, 6%, 6.5%, 7%, 7.5%,
8%th, 8.5%, 9%, 9.2%, 9.4%, 9.6%, 9.8%, 10.0%, 10.2%, 10.4%, 10.6%, 10.8%,
11.0%th, 11.2%, 11.4%, 11.6%, 11.8%, 12.0%, 12.2%, 12.4%, 12.6%, 12.8%, 13.0%,
13.2%th, 13.4%, 13.6%, 13.8%, 14.0%, 14.2%, 14.4%, 14.6%, 14.8%, 15.0%, 15.2%,
15.4%th, 15.6%, 15.8%, 16.0%, 16.5%, 17.0%, 17.5%, 18.0%, 18.5%, 19.0%, 19.5%,
20.0%th, 20.5%, 21.0%, 21.5%, 22.0%, 22.5%, 23.0%, 23.5%, 24.0%, 24.5%, 25.0%,
25.5%th, 26.0%wt etc., or cited arbitrary value combines the scope to be formed.In various implementation methods of the invention
In, the content of copper preferably accounts for 9.0~16.0wt% of catalyst weight, more preferably accounts for 9.2~11.4wt% of catalyst weight.
The content of alkali metal of the present invention can be in 0.2~4.0wt% scopes in arbitrary value or the scope
Arbitrary value combines the scope to be formed, such as 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%,
1.0%th, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2.0%, 2.1%,
2.2%th, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9%, 3.0%, 3.1%, 3.2%, 3.3%,
3.4%th, 3.5%, 3.6%, 3.7%, 3.8%, 3.9%, 4.0%wt etc., or cited arbitrary value combines what is formed
Scope.In the various embodiments of the present invention, the content of alkali metal preferably accounts for 0.5~2.6wt% of catalyst weight, more excellent
Choosing accounts for 0.6~1.1wt% of catalyst weight.
The content of rare earth metal of the present invention can be arbitrary value or the scope in 0.2~2.0wt% scopes
Interior arbitrary value combines the scope to be formed, such as 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%,
1.0%th, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2.0%wt etc., or
Cited arbitrary value combines the scope to be formed.In the various embodiments of the present invention, the content of rare earth metal is preferably accounted for and urged
0.4~1.2wt% of agent weight, more preferably accounts for 0.6~1.2wt% of catalyst weight.
The content of ruthenium of the present invention can be any in arbitrary value or the scope in 2.0~8.0wt% scopes
Value combination formed scope, such as 2.0%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%,
2.9%th, 3.0%, 3.1%, 3.2%, 3.3%, 3.4%, 3.5%, 3.6%, 3.7%, 3.8%, 3.9%, 4.0%,
4.1%th, 4.2%, 4.3%, 4.4%, 4.5%, 4.6%, 4.7%, 4.8%, 4.9%, 5.0%, 5.1%, 5.2%,
5.3%th, 5.4%, 5.5%, 5.6%, 5.7%, 5.8%, 5.9%, 6.0%, 6.1%, 6.2%, 6.3%, 6.4%,
6.5%th, 6.6%, 6.7%, 6.8%, 6.9%, 7.0%, 7.1%, 7.2%, 7.3%, 7.4%, 7.5%, 7.6%,
7.7%th, 7.8%, 7.9%, 8.0%wt etc., or cited arbitrary value combines the scope to be formed.Of the invention various
In implementation method, the content of ruthenium preferably accounts for 2.5~5.0wt% of catalyst weight, more preferably account for catalyst weight 3.0~
5.0wt%.
Alkali metal of the present invention is selected from lithium, sodium, potassium, rubidium, caesium, francium.
Rare earth metal of the present invention is selected from scandium (Sc), yttrium (Y), lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium
(Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), lutetium (Lu).
The present invention further relates to a kind of prepare catalyst for catalysis oxidation hydrogen chloride production chlorine in another aspect
Method, comprising：
A) by copper-containing compound, alkali metal-containing compound and it is dissolved in first liquid containing rare earth compound and is made first
Solution, to addition carrier and first impregnation in first solution；
B) filter off first solution and obtain the carrier that first impregnation is crossed, first drying simultaneously calcines the first impregnation for the first time
The carrier crossed is so as to obtain first burnt carrier；
C) it is dissolved in containing ruthenium compound and the second solution is made in second liquid, the addition first burnt carrier is simultaneously secondary
Dipping；
D) filter off second solution and obtain the carrier that double-steeping is crossed, dry again and calcine the double-steeping again
The carrier crossed is so as to obtain catalyst.
In the various embodiments of the present invention, the copper-containing compound is selected from Cu oxide and/or chloride, the copper
Oxide be selected from cupric oxide, cuprous oxide or one or more mixture, copper chloride be selected from copper chloride, stannous chloride or
The mixture of one or more.In the various embodiments of the present invention, the copper-containing compound can be the salt of hydration.
The mixing that ruthenic chloride, ruthenium-oxide, oxychlorination ruthenium, nitric acid ruthenium or one or more are selected from containing ruthenium compound
Thing, preferably ruthenic chloride.In the various embodiments of the present invention, described can be the salt being hydrated containing ruthenium compound.
The alkali metal-containing compound is selected from the mixing of potassium chloride, sodium chloride, potassium nitrate, sodium nitrate or one or more
Thing, preferably potassium chloride.In the various embodiments of the present invention, the alkali metal-containing compound can be the salt of hydration.
The chloride or nitrate that lanthanum or cerium are selected from containing rare earth compound, or one or more mixing
Thing, preferably cerium chloride.In the various embodiments of the present invention, described can be the salt being hydrated containing rare earth compound.
The carrier is selected from alundum (Al2O3), titanium dioxide, tin oxide, silica, zirconium oxide or one or more
Mixture, preferably alundum (Al2O3), most preferably γ-alundum (Al2O3).
The first impregnation and the double-steeping can be with identical or different.The first impregnation or the double-steeping
Time is 6-15 hours, preferably 8-12 hours.The first impregnation or the double-steeping are preferably impregnated using ultrasonic assistant,
Wherein first impregnation when, ultrasonic assistant dip time be 5~30 minutes, preferably 10~20 minutes；Or during double-steeping,
Ultrasonic assistant dip time is 20~60 minutes, preferably 30~50 minutes.As it is known by the man skilled in the art that in the present invention
Suitable first impregnation and the time of double-steeping can be determined by mode well known to those skilled in the art.
The first liquid or second liquid may be selected from distilled water, dust technology, watery hydrochloric acid etc..
The temperature of the first calcining is 300~700 DEG C, and preferably 350~450 DEG C, the time is 3~6 hours；It is preferred that 4~5
Hour.The first calcining is preferably carried out in air atmosphere.As it is known by the man skilled in the art that suitable first in the present invention
The time of calcining and temperature can be determined by mode well known to those skilled in the art.
The temperature calcined again is 200600 DEG C, and preferably 300~500 DEG C, the time is 2~5 hours；It is preferred that 2~3 is small
When.Described calcining again is preferably carried out in air atmosphere.As it is known by the man skilled in the art that suitable in the present invention forge again
The time of burning and temperature can be determined by mode well known to those skilled in the art.
The condition of the first drying is：Temperature is 100~130 DEG C, and preferably 120 DEG C, the time is 0.5~16h, is extremely existed
It is weightless under the conditions of 120 DEG C of dryings 1 hour≤1% to terminate.
The condition dried again is：Temperature is 100~130 DEG C, and preferably 120 DEG C, the time is 0.5~16h, is extremely existed
It is weightless under the conditions of 120 DEG C of dryings 1 hour≤1% to terminate.
The present invention further relates to a kind of method of catalysis oxidation hydrogen chloride production chlorine in another aspect, including：
A) containing hydrogen chloride feed gas stream and the oxygenous logistics for aoxidizing the hydrogen chloride are supplied；
B) by the containing hydrogen chloride feed gas stream and for aoxidizing the oxygenous logistics of the hydrogen chloride with the present invention
The catalyst contact is reacted；
C) separated from the logistics reacted and obtain chlorine.
Containing hydrogen chloride unstripped gas of the present invention includes being produced from relevant industries production, the acyl chlorides of such as isocyanates
Production, aromatic compounds chlorination etc. by-product form hydrogen chloride.The hydrogen chloride of the by-product form can be by
The byproduct hydrogen chloride of preliminary treatment or the byproduct hydrogen chloride directly from relevant industries without any treatment.
Oxygenous logistics of the present invention can be that the gas or other oxygen-containing gas of pure form are (such as empty
Gas).
The method of the invention can be carried out using continuous or intermittent reaction mode, it is preferred to use successive reaction mode.
The present invention further relates to the catalyst for the purposes of catalysis oxidation hydrogen chloride production chlorine, bag in another aspect
Include：Containing hydrogen chloride feed gas stream and oxygenous logistics for aoxidizing the hydrogen chloride are connect with catalyst of the present invention
Touch and reacted.
Catalyst of the present invention have under low reaction temperatures keep high activity, change over time stability beneficial effect high
Really.Specifically, catalyst of the present invention significantly improves the activity of catalyst, and the catalytic capability of each component can be made to obtain maximum limit
The utilization of degree, while eliminating catalyst loss caused by catalyst hot-spot, improves the heat during catalyst use
Stability.The preparation method of catalyst of the present invention improves the stability of catalyst using infusion process twice.The present invention is using super
Sound wave assistant soakage, ultrasound can promote catalyst activity component in the dispersion of catalyst surface, and distribution is more uniform, and can promote
Enter the increase of catalyst surface active constituent content.By the catalyst of the method preparation in catalytic oxidation process, relatively low
During temperature, the oxidation susceptibility of ruthenium can be given full play to, and the burnt formation ruthenium-oxide containing ruthenium compound is coated on the table of copper
Face.As exothermic heat of reaction, temperature are raised, the high-temperature catalytic performance of copper is played, and the shell that simultaneous oxidation ruthenium is formed can be prevented again
The loss of copper.In the fixed bed or fluid bed that temperature is 300 DEG C~420 DEG C, chlorine can be realized by using catalyst of the present invention
Change hydrogen conversion ratio more than 90%, or the reaction mixture gas that chlorine content more than 50% can be obtained.
Below, the application will be illustrated with specific embodiment.These specific embodiments be all it is exemplary, without
It is restricted.By the comparing between these embodiments and comparative example, those skilled in the art are able to recognize that this hair
It is bright with unexpected technique effect.
Specific embodiment
Embodiment 1
Catalyst preparation：A) by 2.5 grams of Copper dichloride dihydrate, 0.20 gram of potassium chloride and the seven of 0.25 gram hydration trichlorines
Change during cerium is added to appropriate distilled water and be made the first solution, to adding carrier and first impregnation 8 hours in first solution；
B) filter off first solution and obtain the carrier that first impregnation is crossed, first drying is simultaneously calcined for the first time through 400 DEG C of temperature
The carrier that the first impregnation is crossed is so as to obtain first burnt carrier；
C) the second solution is made with the compound of two hydrate ruthenium trichlorides of 1.0 grams of water dissolves of distillation, is added described first
Burnt carrier and double-steeping 8 hours；
D) filter off second solution and obtain the carrier that double-steeping is crossed, after drying again and at a temperature of 400 DEG C again
Carrier that the double-steeping crosses is calcined so as to obtain catalyst.
Drawn through elementary analysis：Copper accounts for the 5.2% of catalyst weight in catalyst, and potassium accounts for the 0.5% of catalyst weight, dilute
Earth metal cerium accounts for the 0.4% of catalyst weight, and ruthenium accounts for the 2.5% of catalyst weight.
Embodiment 2
The preparation method of catalyst such as embodiment 1.
Copper dichloride dihydrate：4.5 grams
Potassium chloride：0.25 gram
Cerous chloride heptahydrate：0.30 gram
Two hydrate ruthenium trichlorides：1.85 grams
Drawn through elementary analysis：Copper accounts for the 9.2% of catalyst weight in catalyst, and potassium accounts for the 0.6% of catalyst weight, dilute
Earth metal cerium accounts for the 0.5% of catalyst weight, and ruthenium accounts for the 5.0% of catalyst weight.
Embodiment 3
The preparation method of catalyst such as embodiment 1.
Copper dichloride dihydrate：8.0 grams
Potassium chloride：0.60 gram
Cerous chloride heptahydrate：0.80 gram
Two hydrate ruthenium trichlorides：1.2 grams
Drawn through elementary analysis：Copper accounts for the 17.0% of catalyst weight in catalyst, and potassium accounts for the 1.5% of catalyst weight,
Rare earth metal cerium accounts for the 1.4% of catalyst weight, and ruthenium accounts for the 2.8% of catalyst weight.
Embodiment 4
The preparation method of catalyst such as embodiment 1.
Copper dichloride dihydrate：10 grams
Potassium chloride：0.70 gram
Cerous chloride heptahydrate：0.65 gram
Two hydrate ruthenium trichlorides：2.0 grams
Drawn through elementary analysis：Copper accounts for the 24.0% of catalyst weight in catalyst, and potassium accounts for the 3.0% of catalyst weight,
Rare earth metal cerium accounts for the 1.0% of catalyst weight, and ruthenium accounts for the 5.0% of catalyst weight.
Embodiment 5
The preparation method of catalyst such as embodiment 1.
Copper dichloride dihydrate：6.0 grams
Potassium chloride：0.40 gram
Cerous chloride heptahydrate：0.40 gram
Two hydrate ruthenium trichlorides：1.5 grams
Drawn through elementary analysis：Copper accounts for the 12.0% of catalyst weight in catalyst, and potassium accounts for the 1.1% of catalyst weight,
Rare earth metal cerium accounts for the 0.6% of catalyst weight, and ruthenium accounts for the 3.5% of catalyst weight.
Embodiment 6
The preparation method of catalyst such as embodiment 1.
Copper dichloride dihydrate：6.0 grams
Potassium chloride：0.3 gram
Cerous chloride heptahydrate：0.85 gram
Two hydrate ruthenium trichlorides：1.8 grams
Drawn through elementary analysis：Copper accounts for the 11.3% of catalyst weight in catalyst, and potassium accounts for the 0.8% of catalyst weight,
Rare earth metal cerium accounts for the 1.2% of catalyst weight, and ruthenium accounts for the 4.1% of catalyst weight.
Embodiment 7
The preparation method of catalyst such as embodiment 1.
Copper dichloride dihydrate：7.5 grams
Potassium chloride：1.0 grams
Cerous chloride heptahydrate：0.8 gram
Two hydrate ruthenium trichlorides：2.0 grams
Drawn through elementary analysis：Copper accounts for the 15.2% of catalyst weight in catalyst, and potassium accounts for the 2.6% of catalyst weight,
Rare earth metal cerium accounts for the 1.2% of catalyst weight, and ruthenium accounts for the 4.8% of catalyst weight.
Embodiment 8
The preparation method of catalyst such as embodiment 1.
Copper dichloride dihydrate：5 grams
Potassium chloride：0.3 gram
Cerous chloride heptahydrate：0.3 gram
Two hydrate ruthenium trichlorides：：1.3 grams
Drawn through elementary analysis：Copper accounts for the 9.2% of catalyst weight in catalyst, and potassium accounts for the 0.6% of catalyst weight, dilute
Earth metal cerium accounts for the 0.5% of catalyst weight, and ruthenium accounts for the 3.0% of catalyst weight.
Comparative example 1
The preparation method of catalyst such as embodiment 1.
Copper dichloride dihydrate：2.5 grams
Potassium chloride：0.15 gram
Cerous chloride heptahydrate：0.25 gram
Two hydrate ruthenium trichlorides：6.0 grams
Drawn through elementary analysis：The content of catalyst copper accounts for the 5.6% of catalyst weight, the content of potassium metallic element
The 0.5% of catalyst weight is accounted for, the content of rare earth metal Ce elements accounts for the 0.4% of catalyst weight, and the content of ruthenium element is accounted for urges
The 15.2% of agent weight.
Comparative example 2
The preparation method of catalyst such as embodiment 1.
Copper dichloride dihydrate：14.0 grams
Potassium chloride：0.2 gram
Cerous chloride heptahydrate：0.35 gram
Two hydrate ruthenium trichlorides：2.0 grams
Drawn through elementary analysis：Copper accounts for the 30.3% of catalyst weight in catalyst, and potassium accounts for the 0.6% of catalyst weight,
Rare earth metal cerium accounts for the 0.6% of catalyst weight, and ruthenium accounts for the 5.2% of catalyst weight.
Comparative example 3
9.0 grams of Copper dichloride dihydrate, 1.0 grams of potassium chloride are added in appropriate distilled water and are made solution, added
Carrier impregnation 8 hours；Solution is filtered out after the completion of dipping, impregnated carrier is first dried, is obtained by 400 DEG C of temperature calcinations
Catalyst.Drawn through elementary analysis：Copper accounts for the 17.2% of catalyst weight in catalyst, and potassium accounts for the 1.5% of catalyst weight.
Comparative example 4
The preparation method of catalyst such as embodiment 1.
9.0 grams of Copper dichloride dihydrate, the potassium chloride of 1.0 gram quantity and 0.7 gram of Cerous chloride heptahydrate are added to suitable
Solution is made in the distilled water of amount, carrier impregnation is added 8 hours；Impregnated carrier is first dried, by 400 DEG C of temperature calcinations
Obtain catalyst.Drawn through elementary analysis：Copper accounts for the 16.8% of catalyst weight in catalyst, and potassium accounts for catalyst weight
1.5%, rare earth metal cerium accounts for the 1.5% of catalyst weight
Comparative example 5
By 9.0 grams of Copper dichloride dihydrate, 1.0 grams of potassium chloride, 0.7 gram of Cerous chloride heptahydrate and 1.3 gram quantity
Two chloride hydrate rutheniums are made solution in being added to appropriate distilled water, add carrier impregnation 8 hours；Impregnated carrier is first dried
Do, obtain catalyst by 400 DEG C of temperature calcinations.Drawn through elementary analysis：Copper accounts for the 17.0% of catalyst weight in catalyst,
Potassium accounts for the 1.5% of catalyst weight, and rare earth metal cerium accounts for the 1.4% of catalyst weight, and ruthenium accounts for the 2.8% of catalyst weight.
Comparative example 6
1.3 grams of two hydrate ruthenium trichlorides are added to solution is made in appropriate distilled water, add carrier impregnation 8 small
When；Impregnated carrier is first dried, first burnt carrier is obtained by 400 DEG C of temperature calcinations；With distillation water dissolves 9.0
Gram Copper dichloride dihydrate compound, 1.0 grams of potassium chloride and 0.7 gram of Cerous chloride heptahydrate compound be made it is molten
Liquid, first burnt carrier impregnation 8 hours, calcine and are catalyzed again after drying through 400 DEG C of temperature in addition the present embodiment
Agent.Drawn through elementary analysis：The 17.0% of copper catalyst weight in catalyst, potassium accounts for the 1.5% of catalyst weight, rare earth metal
Cerium accounts for the 1.4% of catalyst weight, and ruthenium accounts for the 2.8% of catalyst weight.
Above-mentioned catalyst is measured：
Catalysis oxidation hcl reaction is carried out in fixed bed reactors, catalyst, bed temperature liter are added in reactor
Temperature to 360 DEG C when, lead to hydrogen chloride and oxygen, flow be respectively 40ml/ minute, 20ml/ minute when, reaction maintenance 2 hours after, use
100ml concentration be 30% KI solution absorb 5 minutes, with the Na for having demarcated2S2O3The C1 of solution titration generation2.Calculate HCl's
The content of conversion ratio and chlorine in reaction gas, as a result as shown in table 1：
Table 1
Choose the catalyst of embodiment 7, the measure of the stability that work is further changed over time.Enter in fixed bed reactors
Row catalysis oxidation hcl reaction, adds catalyst in reactor, when bed temperature is warmed up to 360 DEG C, lead to hydrogen chloride and oxygen,
Flow be respectively 40ml/ minutes, 20ml/ minutes when, respectively determine reaction maintain 2h, 80h, 168h, 309h, 452h, 600h when,
The conversion ratio and chlorine content of HCl, assay method is：Absorbed 5 minutes with KI solution that 100ml concentration is 30%, with having demarcated
Na2S2O3The Cl of solution titration generation2.The content of the conversion ratio and chlorine of HCl in reaction gas is calculated, as a result such as the institute of table 2
Show：
Table 2：The catalyst performance of embodiment 7 is tested
| Reaction time/h | HCl conversion ratios (%) | Chlorine content (%) |
| 2 | 96.5 | 62.3 |
| 80 | 94.9 | 60.3 |
| 168 | 97.1 | 62.8 |
| 309 | 95.6 | 61.0 |
| 452 | 95.7 | 61.2 |
| 600 | 96.7 | 62.5 |
Choose the catalyst of embodiment 8, the measure of the stability that work is further changed over time.Enter in fixed bed reactors
Row catalysis oxidation hcl reaction, adds catalyst in reactor, when bed temperature is warmed up to 360 DEG C, lead to hydrogen chloride and oxygen,
Flow be respectively 40ml/ minutes, 20ml/ minutes when, respectively determine reaction maintain 2h, 76h, 180h, 345h, 538h, 820h when,
The conversion ratio and chlorine content of HCl, assay method is：Absorbed 5 minutes with KI solution that 100ml concentration is 30%, with having demarcated
Na2S2O3The Cl of solution titration generation2.The content of the conversion ratio and chlorine of HCl in reaction gas is calculated, as a result such as the institute of table 3
Show：
Table 3：The catalyst performance of embodiment 8 is tested
| Reaction time/h | HCl conversion ratios (%) | Chlorine content (%) |
| 2 | 98.0 | 64.1 |
| 76 | 96.4 | 62.0 |
| 180 | 97.5 | 63.5 |
| 345 | 95.2 | 60.6 |
| 538 | 95.8 | 61.3 |
| 820 | 96.9 | 62.7 |
Claims (57)
1. a kind of catalyst for catalysis oxidation hydrogen chloride production chlorine, wherein containing ruthenium, copper, alkali metal and rare earth metal group
Point, it is characterised in that：The content of copper accounts for 3.0~26.0wt% of catalyst weight；The content of alkali metal accounts for catalyst weight
0.2~4.0wt%；The content of rare earth metal accounts for 0.2~2.0wt% of catalyst weight；The content of ruthenium accounts for catalyst weight
2.0~8.0wt%.
2. catalyst according to claim 1, the content of wherein copper accounts for 9.0~16.0wt% of catalyst weight.
3. catalyst according to claim 1, the content of wherein copper accounts for 9.2~11.4wt% of catalyst weight.
4. catalyst according to claim 1, the content of wherein alkali metal accounts for 0.5~2.6wt% of catalyst weight.
5. catalyst according to claim 1, the content of wherein alkali metal accounts for 0.6~1.1wt% of catalyst weight.
6. catalyst according to claim 1, the content of wherein rare earth metal accounts for 0.4~1.2wt% of catalyst weight.
7. catalyst according to claim 1, the content of wherein rare earth metal accounts for 0.6~1.2wt% of catalyst weight.
8. catalyst according to claim 1, the content of wherein ruthenium accounts for 2.5~5.0wt% of catalyst weight.
9. catalyst according to claim 1, the content of wherein ruthenium accounts for 3.0~5.0wt% of catalyst weight.
10. the catalyst according to claim any one of 1-9, wherein alkali metal are selected from lithium, sodium, potassium, rubidium, caesium, francium.
11. catalyst according to claim any one of 1-9, wherein rare earth metal be selected from scandium, yttrium, lanthanum, cerium, praseodymium, neodymium,
Promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium.
12. catalyst according to claim any one of 1-9, wherein also including carrier, the carrier is selected from three oxidations two
The mixture of aluminium, titanium dioxide, tin oxide, silica, zirconium oxide or one or more.
13. catalyst according to claim 12, wherein the carrier is alundum (Al2O3).
14. catalyst according to claim 13, wherein the carrier is γ-alundum (Al2O3).
A kind of 15. methods for preparing the catalyst described in claim any one of 1-14, comprising：
A) it is dissolved in first liquid that to be made first molten by copper-containing compound, alkali metal-containing compound and containing rare earth compound
Liquid, to addition carrier and first impregnation in first solution；
B) filter off first solution and obtain the carrier that first impregnation is crossed, first drying simultaneously calcines what the first impregnation was crossed for the first time
Carrier is so as to obtain first burnt carrier；
C) it is dissolved in containing ruthenium compound and the second solution is made in second liquid, adds the first burnt carrier and secondary leaching
Stain；
D) filter off second solution and obtain the carrier that double-steeping is crossed, dry again and calcine what the double-steeping was crossed again
Carrier is so as to obtain catalyst.
16. methods according to claim 15, wherein the copper-containing compound is selected from Cu oxide and/or chloride.
17. methods according to claim 16, wherein the Cu oxide be selected from cupric oxide, cuprous oxide or its it is a kind of or
Various mixtures.
18. methods according to claim 16, wherein the copper chloride be selected from copper chloride, stannous chloride or its it is a kind of or
Various mixtures.
19. methods according to claim 15, wherein the copper-containing compound can be the salt of hydration.
20. method according to claim any one of 15-18, wherein it is described containing ruthenium compound be selected from ruthenic chloride, ruthenium-oxide,
The mixture of oxychlorination ruthenium, nitric acid ruthenium or one or more.
21. methods according to claim 20, wherein described is ruthenic chloride containing ruthenium compound.
22. methods according to claim 21, wherein described can be the salt of hydration containing ruthenium compound.
23. method according to claim any one of 15-18, wherein the alkali metal-containing compound is selected from potassium chloride, chlorine
Change the mixture of sodium, potassium nitrate, sodium nitrate or one or more.
24. methods according to claim 23, wherein the alkali metal-containing compound is potassium chloride.
25. method according to claim any one of 15-18, wherein the alkali metal-containing compound can be hydration
Salt.
26. method according to claim any one of 15-18, wherein described be selected from lanthanum or cerium containing rare earth compound
Chloride or nitrate, or one or more mixture.
27. methods according to claim 26, wherein described is cerium chloride containing rare earth compound.
28. method according to claim any one of 15-18, wherein described can be hydration containing rare earth compound
Salt.
29. method according to claim any one of 15-18, wherein the carrier be selected from alundum (Al2O3), titanium dioxide,
The mixture of tin oxide, silica, zirconium oxide or one or more.
30. methods according to claim 29, wherein the carrier is alundum (Al2O3).
31. methods according to claim 30, wherein the carrier is γ-alundum (Al2O3).
32. method according to claim any one of 15-18, wherein the time of the first impregnation or the double-steeping
It is 6~15 hours.
33. methods according to claim 32, wherein the time of the first impregnation or the double-steeping is 8~12 small
When.
34. method according to claim any one of 15-18, wherein the first impregnation is impregnated using ultrasonic assistant,
Wherein first impregnation when, ultrasonic assistant dip time be 5~30 minutes.
35. methods according to claim 34, wherein the ultrasonic assistant dip time is 10~20 minutes.
36. method according to claim any one of 15-18, wherein the double-steeping is impregnated using ultrasonic assistant,
Wherein double-steeping when, ultrasonic assistant dip time be 20~60 minutes.
37. methods according to claim 36, wherein ultrasonic assistant dip time are 30~50 minutes.
38. method according to claim any one of 15-18, wherein the first liquid or second liquid may be selected from distillation
Water, dust technology, watery hydrochloric acid.
39. method according to claim any one of 15-18, wherein the temperature of the first calcining is 400~800 DEG C,
Time is 2~5 hours.
40. method according to claim 39, wherein the temperature of the first calcining is 500~600 DEG C.
41. method according to claim 39, wherein the time of the first calcining is 2~3 hours.
42. method according to claim 39, wherein the first calcining is carried out in air atmosphere.
43. method according to claim any one of 15-18, wherein the temperature calcined again is 200~600 DEG C,
Time is 2~5 hours.
44. methods according to claim 43, wherein the temperature calcined again is 300~500 DEG C.
45. methods according to claim 43, wherein the time calcined again is 2~3 hours.
46. methods according to claim 43, wherein described calcining again is carried out in air atmosphere.
47. method according to claim any one of 15-18, wherein the condition of the first drying is：Temperature be 100~
130 DEG C, the time is 0.5~16h.
48. methods according to claim 47, wherein the condition of the first drying is：Temperature is 120 DEG C.
49. method according to claim any one of 15-18, wherein the condition dried again is：Temperature be 100~
130 DEG C, the time is 0.5~16h.
50. methods according to claim 49, wherein the condition dried again is：Temperature is 120 DEG C.
A kind of 51. methods of catalysis oxidation hydrogen chloride production chlorine, including：
A) containing hydrogen chloride feed gas stream and the oxygenous logistics for aoxidizing the hydrogen chloride are supplied；
B) by the containing hydrogen chloride feed gas stream and for aoxidizing the oxygenous logistics of the hydrogen chloride and claim 1-8
Catalyst contact described in any one is reacted；
C) separated from the logistics reacted and obtain chlorine.
52. according to the method for claim 51, wherein described containing hydrogen chloride unstripped gas includes the production from isocyanates, acyl
The production of chlorine, the hydrogen chloride of the by-product form of aromatic compounds chlorination.
53. according to the method for claim 51 or 52, the oxygenous logistics described in it can be pure form gas or
Other oxygen-containing gas.
54. according to the method for claim 53, wherein described other oxygen-containing gas are air.
55. can be carried out according to the method for claim 51 or 52, wherein methods described using continuous or intermittent reaction mode.
56. use successive reaction mode according to the method for claim 55, wherein methods described.
Catalyst described in 57. claim any one of 1-14 is used for the purposes of catalysis oxidation hydrogen chloride production chlorine, including：To contain
Hydrogen chloride feed gas stream and the oxygenous logistics for aoxidizing the hydrogen chloride are urged with described in claim any one of 1-14
Agent contact is reacted.
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| CN105289631B (en) * | 2015-11-25 | 2020-10-30 | 上海氯碱化工股份有限公司 | Catalyst for preparing chlorine by catalytic oxidation of hydrogen chloride and preparation method and application thereof |
| CN105879866A (en) * | 2016-05-03 | 2016-08-24 | 中国科学院大学 | Efficient Deacon reaction catalyst |
| CN107684927B (en) * | 2016-08-03 | 2020-07-28 | 万华化学集团股份有限公司 | Catalyst for preparing chlorine by hydrogen chloride oxidation and preparation method and application thereof |
| CN107952436B (en) * | 2016-10-14 | 2019-12-10 | 中国石油化工股份有限公司 | Copper-zirconium-based catalyst for preparing chlorine by oxidizing hydrogen chloride and preparation method and application thereof |
| CN106861714B (en) * | 2017-02-09 | 2019-08-27 | 西安近代化学研究所 | A kind of catalyst of hydrogen chloride conversion preparing chlorine gas |
| CN106890666B (en) * | 2017-02-09 | 2019-06-28 | 西安近代化学研究所 | A kind of catalyst of hydrogen chloride Efficient Conversion preparing chlorine gas |
| CN108144632B (en) * | 2018-01-22 | 2020-11-03 | 西安元创化工科技股份有限公司 | Ruthenium dioxide catalyst for methane oxychlorination and preparation method thereof |
| CN109718789B (en) * | 2018-12-29 | 2022-02-15 | 万华化学集团股份有限公司 | Core-shell structure supported catalyst and preparation method thereof |
| CN110801842A (en) * | 2019-11-26 | 2020-02-18 | 上海氯碱化工股份有限公司 | Catalyst for preparing chlorine gas by catalytic oxidation of hydrogen chloride and preparation method and application thereof |
| CN111203229A (en) * | 2020-02-19 | 2020-05-29 | 中国科学院过程工程研究所 | Preparation method and application of supported composite oxide catalyst |
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| CN1684903A (en) * | 2002-09-26 | 2005-10-19 | 巴斯福股份公司 | Catalyst for the catalytic oxidation of hydrogen chloride |
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| CN1684903A (en) * | 2002-09-26 | 2005-10-19 | 巴斯福股份公司 | Catalyst for the catalytic oxidation of hydrogen chloride |
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