CN108262072A - It is a kind of for catalyzed by ruthenium complexes agent of acetylene hydrochlorination and its preparation method and application - Google Patents
It is a kind of for catalyzed by ruthenium complexes agent of acetylene hydrochlorination and its preparation method and application Download PDFInfo
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- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
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- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
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- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
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Abstract
The invention discloses a kind of for catalyzed by ruthenium complexes agent of acetylene hydrochlorination and preparation method thereof, catalyst of the present invention, which is characterized in that using activated carbon as catalyst carrier, load RuCl3And organic ligand；RuCl3Molar ratio with organic ligand is 1:16, and Ru accounts for 0.1~5.0wt% of overall catalyst weight；The organic ligand is one or more of triphenylphosphine, pyridine, 2,2 ' bipyridyls, acetylacetone,2,4-pentanedione, Chlorodiphenylphosphine, chlorobenzene, cyclopentadiene, 4 cymols, 1,5 cyclo-octadiene.The catalyst preparation process of the present invention is simple, greatly improves the catalytic activity and stability of catalyst, and catalyst is more friendly to environment, and economy is high.
Description
Technical field
The present invention relates to ruthenium catalyst fields, and in particular to a kind of catalyzed by ruthenium complexes agent for acetylene hydrochlorination and its
Preparation method and application.
Background technology
With the development of world economy and the enhancing of environmental protection consciousness, polyvinyl chloride (PVC) is needed as excellent plastics
Ask increasing.The method of production vinyl chloride (VCM) in the world, following three kinds are roughly divided into according to the difference of raw material：Acetylene method,
Ethylene process and ethane method.Substantially replaced in petroleum resources than more rich national acetylene method by ethylene process route,
But due to the energy resource structure feature of China's " rich coal, oil-poor, few gas ", the acetylene method route using coal as raw material produces VCM still
Occupy leading position.Using activated carbon supported mercury chloride as the catalyst to catalyzing acetylene hydrogen chloride in present carbide acetylene method
Reaction, mercury active component easily distils loss in the catalyst.According to statistics, often produce 1 ton of PVC about consume 1.02~
1.41kgHgCl2Catalyst (HgCl2Content：10~12wt%), however about 25% HgCl2It is lost in cyclic process.Mercury is
One heavy metal species, there is severe toxicity, generate a concentration of 0.01~0.1mg/L of toxicity, and cannot be degraded by microorganisms, can only be with not
Same valence state, the Transport And Transformation between water, substrate and biology, occurs dispersion and enrichment enters after human body again it is difficult to be metabolized out
It goes, is gathered in liver, kidney and brain, damage nervous system, cause fearful " minamata disease ".According to 2013 in Japan's signature
《Minamata pact》, explicitly point out the production for vinyl chloride monomer, to 2020 when on the basis of 2010 annual consumptions per unit
Product mercury dosage reduces 50%, until eliminating within 2025 the production technology using mercury or mercury compound.Therefore, current mercury urgently to be resolved hurrily
Pollution problem caused by catalyst, the research and development of non-mercury catalyst are extremely urgent.
On the other hand, recent studies indicate that, with AuCl3The Au base catalyst acetylene hydrogen chlorine prepared for presoma
Change reaction, show preferable catalytic activity and conversion ratio so that Au becomes the preferable replacer of Hg catalyst.It is well known that
The price of Au is more expensive, with a very important position in national economy, therefore, it is necessary to which it is other environmental-friendly to develop searching
, novel mercury-free catalyst high performance, cheap and easy to get.Ru is similar to the peripheral electron Path Properties of Au and Hg, and price
Far below Au, so that Ru catalyst more has competitiveness as the replacer of Hg catalyst.With RuCl3For forerunner's system
Standby Ru bases catalyst has preferable catalytic performance, but its activity and stability still need to improve.By being catalyzed reaction machine to it
The research of reason, it is believed that oxidation state ruthenium is the activated centre of catalysis, still, i) the poor Ru of dispersibility is unfavorable for acetylene hydrochlorination work
The raising of property；Ii) active component content is lower, and the activity of catalyst is poorer.And heteroatomic lone pair electrons or ligand in ligand
Skeleton can be such that Ru is stabilized to play the oxidation states of major catalytic with Ru effects, and the Ru of oxidation state is catalyzed as Ru bases
Agent is catalyzed the active domain of the reaction.Therefore, ruthenium how to be made, which to exist with the more highly disperse active domain for playing major catalytic, is
One difficult point.Therefore how to make the dispersion degree higher of active component in Ru base catalyst, and with more more stable active matters
Kind becomes the emphasis further studied.
Invention content
To solve problems of the prior art, the present invention provides a kind of catalyzed by ruthenium complexes for acetylene hydrochlorination
Agent and its preparation method and application.
Specifically, the present invention provides a kind of catalyzed by ruthenium complexes agent for acetylene hydrochlorination, using activated carbon as catalysis
Agent carrier loads RuCl3And organic ligand；
RuCl3Molar ratio with organic ligand is 1:1-6, and Ru accounts for 0.1~5.0wt% of overall catalyst weight；
The organic ligand is triphenylphosphine, pyridine, 2,2 '-bipyridyl, acetylacetone,2,4-pentanedione, Chlorodiphenylphosphine, chlorobenzene, ring
One or more of pentadiene, 4- cymols, 1,5- cyclo-octadiene.
Wherein, the activated carbon is the activated carbon being modified with the hydrochloric acid or nitric acid of the 5-12mol/L of excess volume.Institute
It states and is modified with the hydrochloric acid or nitric acid of the 5-12mol/L of excess volume when referring to be modified activated carbon, with 5-12mol/L
Hydrochloric acid or nitric acid activated carbon is modified, and the volume of used hydrochloric acid or nitric acid be more than to activated carbon volume.
The present invention also provides a kind of preparation method of the catalyzed by ruthenium complexes agent for acetylene hydrochlorination as described above,
Include the following steps：
Activated carbon is placed in in the bottle,suction of sealing simultaneously 1~4h of vacuumize process, then by RuCl3With organic ligand with molten
Agent is added to after being completely dissolved in the activated carbon of vacuum processing, and stops vacuumizing, and is stirred 4~48h at room temperature and is consolidated
Liquid mixture, by the mixture of gained dry 4 at 100-160 DEG C~for 24 hours, obtain urging for the ruthenium complex of acetylene hydrochlorination
Agent.
Wherein, the activated carbon is modified with following methods：By activated carbon, it is added to the 5-12mol/L of excess volume
Concentrated hydrochloric acid or nitric acid in, at room temperature~80 DEG C stir 4~for 24 hours after, filter and PH to 5~7 be washed with deionized, then
By the activated carbon handled well dry 4 at 100~160 DEG C~for 24 hours.
In addition, the solvent is water, ethyl alcohol, normal propyl alcohol, isopropanol, n-butanol, isobutanol, one kind in acetone or several
Kind.
The present invention also provides a kind of applications of the catalyzed by ruthenium complexes agent as described above for acetylene hydrochlorination, are used
In catalyzing acetylene hydrochlorination.
The catalyst of 2ml is taken, at 180 DEG C, acetylene air speed 180h-1, the volume ratio of acetylene and hydrogen chloride is 1:1.15 environment
Under system, with RuCl3It is 50~60% for the catalyst activity prepared by presoma, selectivity is 98~99%；Opposite, this
The catalytic activity of the catalyst of invention is improved largely, and acetylene maximum conversion is close to 100%, and selectivity is more than 99%.
The present invention is carrier using modified activated carbon, is loaded organic Ru complex precursors using the method for wet impregnation
Onto modified activated carbon, obtain more more stable active sites, preparation method process is simple and practicable, catalyst it is environmentally friendly and
Economy is high, which replaces inorganic RuCl using organic ruthenium complex3Presoma is loaded on absorbent charcoal carrier, Ru species
It interacting with Surface Groups of Active Carbons so that active component is anchored on carrier, content higher, and dispersibility is more preferable, from
And the efficient Ru bases catalyst of more high activity and stability is obtained, wherein, Ru accounts for 0.1~5.0wt% of overall catalyst weight.
The catalyst preparation process of the present invention is simple, increases catalyst surface active site, and promote activated carbon table
The interaction of face group and active specy so that active specy is anchored on carrier, content higher, and dispersibility is more preferable,
The catalytic activity and stability of catalyst are greatly improved, and catalyst is more friendly to environment, economy is high.
Description of the drawings
Fig. 1 is the attached drawing for representing the Catalyst Conversion in embodiment 1-10 and comparative example.
Fig. 2 is the attached drawing for representing the selectivity in embodiment 1-10 and comparative example.
Specific embodiment
The detailed content of the present invention is told about by the following examples, and it is the convenience for understanding to provide embodiment, definitely not
The limitation present invention.
Embodiment 1
Prepare a kind of efficient ruthenium composition catalyst for acetylene hydrochlorination：
Step 1 prepares modified activated carbon：3g activated carbons (AC) are weighed, are added to the concentrated hydrochloric acid of the 12mol/L of 100ml
In, after being stirred at room temperature for 24 hours, filter and PH to 5 is washed with deionized, then by the activated carbon handled well at 100 DEG C
Drying for 24 hours, obtains modified absorbent charcoal carrier.
Step 2 prepares efficient Ru composition catalysts：The pumping of sealing will be placed in by the modified activated carbon of gained in step 1
In filter flask and vacuumize process 1h, the RuCl of 0.4651g is then weighed3With the organic ligand pyridine of 1.0641g (pyridine and Ru's
Molar ratio is 6：1) it, is completely dissolved, is added in the activated carbon of vacuum processing with 100ml water, and stop vacuumizing, in room
The lower stirring 4h of temperature obtains solidliquid mixture, and by the mixture of gained, drying for 24 hours, obtains efficiently being used for acetylene hydrogen at 100 DEG C
The efficient ruthenium composition catalyst of chlorination, is denoted as C1.
The catalyst for catalyzing acetylene hydrochlorination is tested, takes the catalyst of 2ml, at 180 DEG C, acetylene air speed
180h-1, the volume ratio of acetylene and hydrogen chloride is 1:Under 1.15 environmental systems, 48h is reacted, conversion of alkyne can reach 68%,
Selectivity is more than 99%.
Embodiment 2
Prepare a kind of efficient ruthenium composition catalyst for acetylene hydrochlorination：
Step 1 prepares modified activated carbon：Weigh 3g activated carbons (AC), in the nitric acid for the 5mol/L for being added to 100ml,
After stirring 4h at 80 DEG C, filter and PH to 7 is washed with deionized, it is then that the activated carbon handled well is dry at 160 DEG C
4h obtains modified absorbent charcoal carrier.
Step 2 prepares efficient Ru composition catalysts：The pumping of sealing will be placed in by the modified activated carbon of gained in step 1
In filter flask and vacuumize process 4h, the RuCl of 0.0685g is then weighed3With the organic ligand triphenylphosphine (triphen of 0.25986g
The molar ratio of base phosphine and Ru are 3：1) it, is completely dissolved, is added in the activated carbon of vacuum processing with 300ml ethyl alcohol, and stopped
It only vacuumizes, stirs 48h at room temperature and obtain solidliquid mixture, the mixture of gained at 160 DEG C is dried into 4h, is obtained efficiently
The efficient ruthenium composition catalyst for acetylene hydrochlorination, be denoted as C2.
The catalyst for catalyzing acetylene hydrochlorination is tested, takes the catalyst of 2ml, at 180 DEG C, acetylene air speed
180h-1, the volume ratio of acetylene and hydrogen chloride is 1:Under 1.15 environmental systems, 48h is reacted, Catalyst Conversion can reach
99%, selectivity is more than 99%.
Embodiment 3
Prepare a kind of efficient ruthenium composition catalyst for acetylene hydrochlorination：
Step 1 prepares modified activated carbon：3g activated carbons (AC) are weighed, are added separately to the nitric acid of the 5mol/L of 100ml
In, after being stirred at room temperature for 24 hours, filter and PH to 7 is washed with deionized, then by the activated carbon handled well at 140 DEG C
Drying for 24 hours, obtains modified absorbent charcoal carrier.
Step 2 prepares efficient Ru composition catalysts：The pumping of sealing will be placed in by the modified activated carbon of gained in step 1
In filter flask and vacuumize process 2h, the RuCl of 0.06604g is then weighed3With organic ligand 2,2 '-bipyridyl of 0.14918g
(molar ratio of 2,2 '-bipyridyl and Ru are 3：1) it, is completely dissolved with 300ml normal propyl alcohols, is added to the activity of vacuum processing
In charcoal, and stop vacuumizing, stir 12h at room temperature and obtain solidliquid mixture, the mixture of gained is dry at 150 DEG C
For 24 hours, it obtains efficiently being used for the efficient ruthenium composition catalyst of acetylene hydrochlorination, is denoted as C3.
The catalyst for catalyzing acetylene hydrochlorination is tested, takes the catalyst of 2ml, at 180 DEG C, acetylene air speed
180h-1, the volume ratio of acetylene and hydrogen chloride is 1:Under 1.15 environmental systems, 48h is reacted, Catalyst Conversion can reach
85%, selectivity is more than 99%.
Embodiment 4
Prepare a kind of efficient ruthenium composition catalyst for acetylene hydrochlorination：
Step 1 prepares modified activated carbon：3g activated carbons (AC) are weighed, are added separately to the nitric acid of the 5mol/L of 100ml
In, after 12h is stirred at room temperature, filters and PH to 7 is washed with deionized, then by the activated carbon handled well at 140 DEG C
Dry 12h, obtains modified absorbent charcoal carrier.
Step 2 prepares efficient Ru composition catalysts：The pumping of sealing will be placed in by the modified activated carbon of gained in step 1
In filter flask and vacuumize process 2h, the RuCl of 0.06493g is then weighed3With the organic ligand acetylacetone,2,4-pentanedione (acetyl of 0.09402g
The molar ratio of acetone and Ru are 3：1) it, is completely dissolved, is added in the activated carbon of vacuum processing with 300ml isopropanols, and
Stopping vacuumizes, and stirs 12h at room temperature and obtains solidliquid mixture, and by the mixture of gained, drying for 24 hours, obtains at 140 DEG C
The efficient efficient ruthenium composition catalyst for being used for acetylene hydrochlorination, is denoted as C4.
The catalyst for catalyzing acetylene hydrochlorination is tested, takes the catalyst of 2ml, at 180 DEG C, acetylene air speed
180h-1, the volume ratio of acetylene and hydrogen chloride is 1:Under 1.15 environmental systems, 48h is reacted, Catalyst Conversion can reach
98%, selectivity is more than 99%.
Embodiment 5
Prepare a kind of efficient ruthenium composition catalyst for acetylene hydrochlorination：
Step 1 prepares modified activated carbon：3g activated carbons (AC) are weighed, are added separately to the nitric acid of the 5mol/L of 100ml
In, after 12h is stirred at room temperature, filters and PH to 7 is washed with deionized, then by the activated carbon handled well at 140 DEG C
Dry 12h, obtains modified absorbent charcoal carrier.
Step 2 prepares efficient Ru composition catalysts：The pumping of sealing will be placed in by the modified activated carbon of gained in step 1
In filter flask and vacuumize process 2h, the RuCl of 0.06438g is then weighed3With the organic ligand Chlorodiphenylphosphine of 0.06848g
(molar ratio of Chlorodiphenylphosphine and Ru are 1：1) it, is completely dissolved with 300ml n-butanols, is added to the work of vacuum processing
Property charcoal in, and stop vacuumizing, stir 12h at room temperature and obtain solidliquid mixture, the mixture of gained is dry at 140 DEG C
For 24 hours, it obtains efficiently being used for the efficient ruthenium composition catalyst of acetylene hydrochlorination, is denoted as C5.
The catalyst for catalyzing acetylene hydrochlorination is tested, takes the catalyst of 2ml, at 180 DEG C, acetylene air speed
180h-1, the volume ratio of acetylene and hydrogen chloride is 1:Under 1.15 environmental systems, 48h is reacted, Catalyst Conversion can reach
95%, selectivity is more than 99%.
Embodiment 6
Prepare a kind of efficient ruthenium composition catalyst for acetylene hydrochlorination：
Step 1 prepares modified activated carbon：Weigh 3g activated carbons (AC), be added separately to 100ml 12mol/L it is dense
In hydrochloric acid, after 12h is stirred at room temperature, filters and PH to 7 is washed with deionized, then by the activated carbon handled well 140
Dry 12h, obtains modified absorbent charcoal carrier at DEG C.
Step 2 prepares efficient Ru composition catalysts：The pumping of sealing will be placed in by the modified activated carbon of gained in step 1
In filter flask and vacuumize process 1h, the RuCl of 0.006181g is then weighed3With the organic ligand chlorobenzene of 0.003354g (chlorobenzene with
The molar ratio of Ru is 1：1) it, is completely dissolved, is added in the activated carbon of vacuum processing with 300ml isobutanols, and stop taking out
Vacuum stirs 12h and obtains solidliquid mixture at room temperature, and by the mixture of gained, drying for 24 hours, obtains efficient at 140 DEG C
For the efficient ruthenium composition catalyst of acetylene hydrochlorination, it is denoted as C6.
The catalyst for catalyzing acetylene hydrochlorination is tested, takes the catalyst of 2ml, at 180 DEG C, acetylene air speed
180h-1, the volume ratio of acetylene and hydrogen chloride is 1:Under 1.15 environmental systems, 48h is reacted, Catalyst Conversion can reach
60%, selectivity is more than 99%.
Embodiment 7
Prepare a kind of efficient ruthenium composition catalyst for acetylene hydrochlorination：
Step 1 prepares modified activated carbon：3g activated carbons (AC) are weighed, are added separately to the nitric acid of the 5mol/L of 100ml
In, after 12h is stirred at room temperature, filters and PH to 7 is washed with deionized, then by the activated carbon handled well at 140 DEG C
Dry 12h, obtains modified absorbent charcoal carrier.
Step 2 prepares efficient Ru composition catalysts：The pumping of sealing will be placed in by the modified activated carbon of gained in step 1
In filter flask and vacuumize process 2h, the RuCl of 0.06335g is then weighed3With the organic ligand cyclopentadiene (ring of 0.020188g
The molar ratio of pentadiene and Ru are 1：1) it, is completely dissolved, is added in the activated carbon of vacuum processing with 300ml acetone, and
Stopping vacuumizes, and stirs 12h at room temperature and obtains solidliquid mixture, and by the mixture of gained, drying for 24 hours, obtains at 140 DEG C
The efficient efficient ruthenium composition catalyst for being used for acetylene hydrochlorination, is denoted as C7.
The catalyst for catalyzing acetylene hydrochlorination is tested, takes the catalyst of 2ml, at 180 DEG C, acetylene air speed
180h-1, the volume ratio of acetylene and hydrogen chloride is 1:Under 1.15 environmental systems, 48h is reacted, Catalyst Conversion can reach
70%, selectivity is more than 99%.
Embodiment 8
Prepare a kind of efficient ruthenium composition catalyst for acetylene hydrochlorination：
Step 1 prepares modified activated carbon：3g activated carbons (AC) are weighed, are added separately to the nitric acid of the 5mol/L of 100ml
In, after 12h is stirred at room temperature, filters and PH to 7 is washed with deionized, then by the activated carbon handled well at 140 DEG C
Dry 12h, obtains modified absorbent charcoal carrier.
Step 2 prepares efficient Ru composition catalysts：The pumping of sealing will be placed in by the modified activated carbon of gained in step 1
In filter flask and vacuumize process 2h, the RuCl of 0.06383g is then weighed3With the organic ligand 4- cymols of 0.0413g
(molar ratio of 4- cymols and Ru are 1：1) it, is completely dissolved with 300 ethyl alcohol, is added to the activity of vacuum processing
In charcoal, and stop vacuumizing, stir 12h at room temperature and obtain solidliquid mixture, the mixture of gained is dry at 100 DEG C
For 24 hours, it obtains efficiently being used for the efficient ruthenium composition catalyst of acetylene hydrochlorination, is denoted as C8.
The catalyst for catalyzing acetylene hydrochlorination is tested, takes the catalyst of 2ml, at 180 DEG C, acetylene air speed
180h-1, the volume ratio of acetylene and hydrogen chloride is 1:Under 1.15 environmental systems, 48h is reacted, Catalyst Conversion can reach
75%, selectivity is more than 99%.
Embodiment 9
Prepare a kind of efficient ruthenium composition catalyst for acetylene hydrochlorination：
Step 1 prepares modified activated carbon：3g activated carbons (AC) are weighed, are added separately to the nitric acid of the 5mol/L of 100ml
In, after 12h is stirred at room temperature, filters and PH to 7 is washed with deionized, then by the activated carbon handled well at 140 DEG C
Dry 12h, obtains modified absorbent charcoal carrier.
Step 2 prepares efficient Ru composition catalysts：The pumping of sealing will be placed in by the modified activated carbon of gained in step 1
In filter flask and vacuumize process 2h, the RuCl of 0.06365g is then weighed3With the organic ligand 1,5- cyclo-octadiene of 0.033195g
(molar ratio of cyclo-octadiene and Ru are 1：1) it, is completely dissolved, is added in the activated carbon of vacuum processing with 300ml ethyl alcohol,
And stop vacuumizing, 12h is stirred at room temperature and obtains solidliquid mixture, and by the mixture of gained, drying for 24 hours, obtains at 150 DEG C
To the efficient efficient ruthenium composition catalyst for being used for acetylene hydrochlorination, it is denoted as C9.
The catalyst for catalyzing acetylene hydrochlorination is tested, takes the catalyst of 2ml, at 180 DEG C, acetylene air speed
180h-1, the volume ratio of acetylene and hydrogen chloride is 1:Under 1.15 environmental systems, 48h is reacted, Catalyst Conversion can reach
70%, selectivity is more than 99%.
Embodiment 10
Prepare a kind of efficient ruthenium composition catalyst for acetylene hydrochlorination：
Step 1 prepares modified activated carbon：3g activated carbons (AC) are weighed, are added separately to the nitric acid of the 5mol/L of 100ml
In, after 12h is stirred at room temperature, filters and PH to 7 is washed with deionized, then by the activated carbon handled well at 140 DEG C
Dry 12h, obtains modified absorbent charcoal carrier.
Step 2 prepares efficient Ru composition catalysts：The pumping of sealing will be placed in by the modified activated carbon of gained in step 1
In filter flask and vacuumize process 2h, the RuCl of 0.0669g is then weighed3, 0.02132g cyclopentadiene and 0.16919g three
(molar ratio is cyclopentadiene to Phenylphosphine：Triphenylphosphine：Ru=1：2：1) it, is completely dissolved, is added to true with 300ml ethyl alcohol
In the activated carbon of vacancy reason, and stop vacuumizing, stir 12h at room temperature and obtain solidliquid mixture, the mixture of gained is existed
Drying for 24 hours, obtains efficiently being used for the efficient ruthenium composition catalyst of acetylene hydrochlorination, is denoted as C10 at 140 DEG C.
The catalyst for catalyzing acetylene hydrochlorination is tested, takes the catalyst of 2ml, at 180 DEG C, acetylene air speed
180h-1, the volume ratio of acetylene and hydrogen chloride is 1:Under 1.15 environmental systems, 48h is reacted, Catalyst Conversion can reach
90%, selectivity is more than 99%.
Comparative example
It prepares with RuCl3For presoma, using activated carbon as the Ru base catalyst of carrier, Ru load capacity is 1wt%；It is made
Preparation Method is：Weigh 0.064g RuCl3, it is dissolved in 10ml water, then the solution is added in 3g activated carbons, in room temperature
After lower stirring for 24 hours, by the mixture of gained, drying for 24 hours, obtains Ru base catalyst, is denoted as Ru/AC at 140 DEG C.
The catalyst for catalyzing acetylene hydrochlorination is being tested, is taking the catalyst of 2ml, at 180 DEG C, acetylene air speed
180h-1, the volume ratio of acetylene and hydrogen chloride is 1:Under 1.15 environmental systems, 48h is reacted, conversion of alkyne drops to 50%, choosing
Selecting property is 98% or so.
Catalyst Conversion in embodiment 1-10 and comparative example is plotted 1, it will be in embodiment 1-10 and comparative example
Selectivity is plotted 2, shown in Fig. 1 and Fig. 2, hence it is evident that it can be seen that the present invention is with RuCl3With with Ru be in certain mol proportion
Organic ligand (triphenylphosphine, pyridine, bipyridyl, acetylacetone,2,4-pentanedione, Chlorodiphenylphosphine, chlorobenzene, cyclopentadiene, 4- methyl are different
Propylbenzene, 1,5- cyclo-octadiene etc.) for presoma, modified activated carbon is carrier for the complex that is formed, it is water, ethyl alcohol, normal propyl alcohol, different
Propyl alcohol, n-butanol, isobutanol or acetone etc. are substantially better than comparative example for the catalytic activity of novel Ru bases catalyst prepared by solvent
In with RuCl3For presoma prepare Ru base catalyst, mainly due to Ru composition catalysts have more active sites,
And active specy interacts with modified activated carbon surface group so that active specy is anchored on carrier, content higher,
It is dispersed more preferable, so as to greatly improve the catalytic activity of catalyst and stability.
Although above in conjunction with attached drawing, invention has been described, and the invention is not limited in above-mentioned specific implementations
Mode, above-mentioned specific embodiment is only schematical rather than restricted, and those of ordinary skill in the art are at this
Under the enlightenment of invention, many variety classes without deviating from the spirit of the invention, can also made with RuCl3Match with organic
The complex or the deformation of Ru composition catalysts directly prepared using the Ru complexs of commercialization as presoma that body is formed, these
It belongs within the protection of the present invention.
Claims (6)
1. a kind of catalyzed by ruthenium complexes agent for acetylene hydrochlorination, which is characterized in that using activated carbon as catalyst carrier, load
RuCl3And organic ligand；
RuCl3Molar ratio with organic ligand is 1:1-6, and Ru accounts for 0.1~5.0wt% of overall catalyst weight；
The organic ligand is triphenylphosphine, pyridine, 2,2 '-bipyridyl, acetylacetone,2,4-pentanedione, Chlorodiphenylphosphine, chlorobenzene, ring penta 2
One or more of alkene, 4- cymols, 1,5- cyclo-octadiene.
2. the catalyzed by ruthenium complexes agent for acetylene hydrochlorination according to claim, which is characterized in that the activated carbon
For the modified activated carbon being modified with the hydrochloric acid or nitric acid of the 5-12mol/L of excess volume.
3. a kind of preparation method of catalyzed by ruthenium complexes agent for acetylene hydrochlorination as described in claims 1 or 2, special
Sign is, includes the following steps：
Activated carbon is placed in in the bottle,suction of sealing simultaneously 1~4h of vacuumize process, then by RuCl3It is complete with organic ligand solvent
It is added to after fully dissolved in the activated carbon of vacuum processing, and stops vacuumizing, stirred 4~48h at room temperature and obtain solid-liquid and mix
Close object, by the mixture of gained dry 4 at 100-160 DEG C~for 24 hours, obtain the catalyzed by ruthenium complexes for acetylene hydrochlorination
Agent.
4. preparation method according to claim 3, which is characterized in that the activated carbon is modified with following methods：It will
Activated carbon is added in the concentrated hydrochloric acid or nitric acid of 5-12mol/L, at -80 DEG C of room temperature after stirring 4~for 24 hours, filter and spend from
Sub- water washing PH to 5-7, then by the activated carbon handled well dry 4 at 100~160 DEG C~for 24 hours.
5. preparation method according to claim 3, which is characterized in that the solvent for water, ethyl alcohol, normal propyl alcohol, isopropanol,
One or more of n-butanol, isobutanol, acetone.
6. a kind of application of the catalyzed by ruthenium complexes agent as claimed in claim 1 or 2 for acetylene hydrochlorination, feature exist
In using it for catalyzing acetylene hydrochlorination.
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| CN109876864A (en) * | 2019-02-14 | 2019-06-14 | 西安凯立新材料股份有限公司 | A kind of super low loading noble metal composite catalyst and preparation method thereof for acetylene hydrochlorination reaction |
| WO2020016555A1 (en) * | 2018-07-16 | 2020-01-23 | University College Cardiff Consultants Ltd | Catalyst |
| CN111644210A (en) * | 2020-06-22 | 2020-09-11 | 新疆兵团现代绿色氯碱化工工程研究中心(有限公司) | Application of composite carrier ruthenium-based catalyst in acetylene hydrochlorination |
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