CN103381369A - Nitrogen doped carbon material loaded catalyst - Google Patents
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Abstract
Belonging to the technical field of catalysts, the invention discloses a nitrogen doped carbon material loaded catalyst. The carbon material can realize nitrogen doping by means of nitrogen containing precursor chemical coupling and other surface modification methods, also a nitrogen source and a carbon source can be introduced simultaneously at high temperature for in situ synthesis of a nitrogen doped carbon material, and then a simple substance or compound of one or more of gold, copper, manganese, potassium or bismuth can be loaded on the nitrogen doped carbon material. The nitrogen doped carbon material loaded mercury-free catalyst involved in the invention has activity and stability obviously superior to those of ordinary carbon material loaded catalysts. Under certain reaction conditions, the activity of the nitrogen doped carbon material loaded catalyst is superior to that of ordinary carbon material loaded catalysts by over 10%. The carbon material and the catalyst disclosed in the invention are green and non-toxic, and have good environmental benefits. The process involved in the invention is simple, economical and feasible.
Description
Technical field
The present invention relates to a kind of catalyst of catalyzing acetylene hydrochlorination, be specifically related to a kind of catalyst of nitrogen-doped carbon material load.This catalyst be the nitrogen-doped carbon material or on the nitrogen-doped carbon material carried metal simple substance and compound, can realize for a long time that high conversion catalyzing acetylene and hydrogen chloride generate VCM, belong to catalyst technical field.
Background technology
Polyvinyl chloride (Polyvinylchloride, PVC) is world's second largest resins for universal use, and the synthetic of VCM (Vinyl Chloride Monomer is called for short VCM) is the core of whole production technology.
Vinyl chloride synthetic mainly contains two approach: ethylene process and carbide.The resource distribution present situation of " oil-poor rich coal " has determined that China's polyvinyl chloride mainly comes from the coal route, and the existing PVC output of China surpasses 70 % and produces by " carbide ".In carbide, the monomer vinyl chloride of polyvinyl chloride reacts and makes by acetylene hydrochlorination.Its main equation is as follows:
CaC
2+2H
2O→C
2H
2↑+Ca(OH)
2
It is 10-12 % mercury chloride (HgCl that traditional processing technology adopts fixed bed to fill the load quality mark
2) activated carbon catalysis acetylene hydrochlorination reaction.Acetylene (C
2h
2) and the addition reaction of hydrogen chloride (HCl) be strong exothermal reaction (Δ H=-124.8 kJmol
-1), the bad heat-transfer capability of fixed bed can't shift out reaction heat, very easily makes lower boiling HgCl
2vapour pressure raises and the volatilization loss.HgCl in fresh mercury catalyst
2content be generally 11-13 %, wherein Hg content is generally 8.5-10 %, the catalyst mercury content after use is about 2-2.5 %, turnover rate is up to 75 %.Part HgCl
2can realize reclaiming, but still have part by waste water, waste gas and dead catalyst entered environment, environment is caused to serious pollution.
Along with the exhaustion day by day of international mercury resource and day by day highlighting of Global Environmental Problems, mercury catalyst has become the bottleneck of restriction PVC Industry development, imperative without the exploitation of mercury type green catalyst.
The research and development of acetylene hydrochlorination catalyst, mainly concentrate on modulation and the research of active component, ignored to a certain extent the improvement of catalyst carrier.The catalyst carrier type of acetylene hydrochlorination industry now is single, is mainly coconut husk charcoal and ature of coal charcoal isoreactivity charcoal, and without too much chemical modification or modification.
Since Ijima in 1991 at Nature 354,56-58. on publish thesis and find CNT (carbon nanotubes, CNTs), after, over more than 20 year, because of it, there is the study hotspot that superior mechanics, electricity, optics and chemical property become nano material in world wide.
Than common, material with carbon element doping nitrogen-atoms, can change carbon atom cloud density on every side, makes it have good electronic conductivity, and its electronic effect also shows unique performance aspect catalysis material.
The nitrogen doping of material with carbon element mainly is divided into outside doping and inner doping.Outside doping, be mainly by covalent effect and realize outside doping.As material with carbon element reflow treatment in nitric acid is obtained to nitro (NO
2) material with carbon element modified, or adopt the ethanol of azodiisobutyronitrile or tetrahydrofuran solution mixings material with carbon element to obtain again the material with carbon element of cyano group (CN) modification after ethanol cleans.React the material with carbon element that can obtain multiple nitrogen-containing functional group or molecular modification by standard chemical.
Equations of The Second Kind is inner doping, and the carbon atom in material with carbon element can be replaced by the nitrogen element, and in heteroatomic layer, doping will change pattern, structure and the electronic property of material with carbon element.
The method that inner doping prepares nitrogen-doped carbon nanometer pipe mainly contains arc process, laser ablation method and chemical vapour deposition technique.The nitrogenous source of chemical vapour deposition technique nitrating has multiple.As far back as 1997, Yudasaka M etc. were at Carbon, and 35 (2): 195-201. delivers with Nickel Phthalocyanine and not only made carbon nitrogen source but also prepared nitrogen-doped carbon nanometer pipe for catalyst.Lee etc. are at Chemical Physics Letters, 2002,359 (1/2): 115-120. reported adopt ammonia to prepare as nitrogenous source CNT---the nitrogen content that this method is general is not high, general≤3%.Can also use is the material of carbon source and nitrogenous source, as benzylamine, acetonitrile and pyridine etc.This method is under inert atmosphere, and the nitrating mass fraction can improve greatly than the method for ammonia.Presoma and temperature all affect the itrogen content of getter with nitrogen doped of CNT, and atmosphere also can play a role to the carbon pipe.Terrones etc. are at AdvancedMaterials, and 1999,11 (8): reported on 655-658 and usingd melamine as presoma, usingd laser ablation cobalt film as catalyst, the Bamboo-shaped nitrogen-doped carbon nanometer pipe that to synthesize nitrogen content under 1050oC be 7at%.Several different methods can realize the inside nitrogen doping of CNT.
The preparation method of common graphite alkene material has mechanical stripping method, chemical oxidization method, crystal epitaxy method, chemical vapour deposition technique, organic synthesis method and CNT stripping method etc.The preparation method of nitrogen-doped graphene is mainly chemical vapour deposition technique, plasma nitriding, arc discharge method etc.These methods need to be carried out usually under high temperature and protective atmosphere, the nitriding process complexity, and the nitrogen element easily runs off, thereby loses its due performance.Preparation method's broadly similar of the preparation method of nitrogen-doped graphene and nitrogen-doped carbon nanometer pipe can grow the nitrogen-doped graphene mainly existed with the graphite nitrogen form by methane and ammonia under the condition of 800 oC left and right; Ajayan etc. are at ACSNano2010, and 4 (11): reported on 6337-6342. and take second cyanogen as presoma, the Cu paper tinsel is made substrate cracking synthetic nitrogen doped graphene under 950 oC.Except the method for the above, also can at high temperature to common graphite alkene, pass into ammonia and form nitrogen-doped graphene, high energy electrothermal way heating ammonia and Graphene synthetic nitrogen doped graphene.
Mesoporous carbon is novel material with carbon element, adopts nano magnesia as carrier, passes into after methane is grown 5 minutes under 950 oC and gets final product with chlorohydric acid pickling.It has large (2000 ~ 3000 m of specific area
2/ g), the characteristics that graphite-structure is good, meso-hole structure is abundant.Pass into ammonia or pyridine together with methane when the preparation mesoporous carbon, can prepare the mesoporous carbon of nitrogen doping simultaneously.Its nitrogen content can be from 0.1%-10% left and right modulation.
CNT and Graphene make carbon nano tube surface have basic sites and pyridine nitrogen structure after introducing nitrogen-atoms, make it likely as solid base catalyst.Can catalytic hydrogenation after the nitrogen-doped carbon nanometer pipe metal supported catalyst, the serial reaction such as ammonia decomposition.But the nitrogen-doped carbon material being applied to the acetylene hydrochlorination reaction does not have report, and relevant open source literature and patent that nitrogen-dopped activated carbon carries out the acetylene hydrochlorination reaction as carrier are also considerably less.
TAIYO KAKEN CO LTD (KURE-C) discloses a kind of with SnCl
2non-precious metal catalyst (JP50082002-A, JP77012683-B) for main active component.This catalyst is with the difference of patent before and document: carrier active carbon is at NH
3in atmosphere 900
o process 6 hours its nitrogen contents under C and brought up to 3.2 % by 0.6 %.With carrier without NH
3the catalyst of processing is compared, 195
othe C hourly space velocity is 50 h
-1the time acetylene conversion ratio bring up to 99 % by 98 %, vinyl chloride selectively by 34 %, improved 100 %.Visible, by carrier NH
3processed load SnCl
2catalyst selectively being significantly improved to vinyl chloride.Sn described in patent and compound boiling point thereof are low, and the stability of catalyst can't be maintained, and do not mention the life problems of catalyst in this series of patents.
As can be seen here, the material with carbon element of nitrogen doping is to promoting the acetylene hydrochlorination reaction effect remarkable.Just as mentioned before, the research of active component mainly is devoted in the research and development of the catalyst without mercury of preparing chloroethylene by acetylene hydrochlorination.
Catalyst without mercury mainly be take metal chloride as active component, take active carbon as catalyst carrier.One of them example is the SnCl that Deng state in 1994 just waits load on the active carbon of report
2-BiCl
3-CuCl ternary metal chloride catalyst.This catalyst is 140
ounder C, conversion ratio can reach 97%, C
2h
2selectively can reach 95 %, initial activity approaches industrial mercury catalyst.Although this catalyst formulation has good laboratory evaluation result, SnCl
2be one and compare HgCl
2more volatile component, after reacting 12 hours, SnCl
2about 40 % that run off, the SnCl of 48 hours about 80%
2run off.Catalyst activity component Yin Gengyi runs off and can't realize industrialization.
The subject matter of base metal salt catalyst is that initial activity is low, or the activity that may cause because of active component volatilization, carbon distribution is low.From published patent, the research and comparison of non-precious metal catalyst is slow; Precious metal salt, as the catalyst of catalyzing acetylene hydrochlorinate, has superior activity, and not volatile, although the price comparison costliness still is subject to the people's attention.
One of them example be the report such as Hutchings with gold chloride (HAuCl
44H
2o) adopt the catalyst of equi-volume impregnating load on active carbon for presoma.The golden amount mark of this catalyst is 1 %, 180
oc and 870 h
-1under air speed, the conversion of alkyne of fresh catalyst can reach 30 %, but due to the cationic strong oxidizing property of gold, catalyst very easily is reduced in course of reaction, affects its life-span.Flood regeneration by chloroazotic acid, the activity of decaying catalyst can be regenerated, and conversion of alkyne is for returning to 22 %.
This catalyst prepares easy, and catalytic activity is good, has solved the regeneration problem of decaying catalyst simultaneously.Although gold loading is than industrial mercury chloride (HgCl
2) low 1 order of magnitude of load capacity of catalyst, but nearly thousand times of the prices of gold to the mercury price, 1% content can't be realized industrialization.
Another example is gold, copper double base metallic catalyst prepared by this elementary employing equi-volume impregnating of East China University of Science Shen.Catalyst gold loading prepared by the method is 0.5%, at 160 oC and 50 h
-1the acetylene air speed under reaction 200 hours, the conversion ratio of catalyst and selectively all higher than 99.5%.Show superior activity and stability.But the method except bibliographical information without follow-up industrialized report.
Tsing-Hua University's chemical industry be sieve state China etc. disclose a kind of composition metal salt catalyst (application number: 201210114021.7), adopt the complexing agent complexation of metal ions such as cyanogen root, thiocyanate radical, can be so that the content of gold, lower than 0.5%, even be low to moderate 0.1%.In test process, catalyst selectively higher than 99.5%, active and stability has significant lifting than the identical gold content catalyst of reporting, this patent has obtained experiment effect preferably in further industrial long period test.
Nitrogen dopant material of the present invention, comprise nitrogen-doped carbon nanometer pipe, nitrogen-doped graphene and nitrogen-dopped activated carbon, and the mode form with covalent bond on carbon material surface through outside doping in preparation process connects nitrogenous functional group; The mode of perhaps adulterating with inside at high temperature passes into nitrogenous precursor and makes carbon atom part and the nitrogen-atoms effect in material with carbon element, realizes the nitrogen doping of carbon carrier.In the nitrogen-doped carbon material, the molar content of nitrogen element can reach 0.1-10.0%.Nitrogen-doped carbon material without Metal Supported self has very superior catalytic activity, and its activity can be at double and even the raising of several times than common material with carbon element.In addition, simple substance or the compound Kaolinite Preparation of Catalyst of one or more elements such as the gold by infusion process load 0.1-5.0%, copper, bismuth, potassium.At different acetylene air speeds and temperature, the catalyst activity of nitrogen-doped carbon carrier load and stability all are better than the catalyst of common carbon carrier load.At 360 h
-1air speed and v (HCl): v (C
2h
2): v (H
2)=1.1:1.0:0.5, under the reaction condition of 180oC and normal pressure, the catalyst activity of doping carbon carrier is better than the catalyst of common carbon carrier load more than 10%.Catalyst disclosed by the invention is green non-poisonous, has good environmental benefit; The technological process simple economy the present invention relates to is feasible.
Summary of the invention
The purpose of content of the present invention is to provide a kind of novel carbon carrier and catalyst without mercury for the deficiency of existing acetylene hydrochlorination catalyst technology.This catalyst, by after carrier is carried out to the chemical modification of nitrogen-doping, can increase activity and the stability of catalyst; In the situation that the noble-metal-supported amount is lower, catalyst still shows good activity, selective and stability.Under reaction temperature, catalyst property is stable, and carbon carrier and activity component metal are nontoxic, does not have the volatilization of running off, and is a kind of eco-friendly catalyst.
A kind of catalyst without mercury of nitrogen-doped carbon material load, described catalyst is without one or more the nitrogen-doped carbon material in Metal Supported or gold-supported, copper, bismuth, manganese or potassium; Described nitrogen-doped carbon material is carbon material surface or bulk phase-doped the nitrogen element is arranged.
In described nitrogen-doped carbon material, the molar content of nitrogen element is 0.1-20.0%.
The mass fraction of described gold in catalyst is 0.05-0.3%; Described copper, bismuth, manganese, the potassium mass fraction in catalyst is respectively 0.05-15.0%; Described gold, copper, bismuth, manganese, potassium exist with one or more states in metal simple-substance, chloride, rhodanide or cyanide;
Described nitrogen-doped carbon material is a kind of in active carbon, CNT, mesoporous carbon, Graphene or more than one.
Described surface or bulk phase-doped the nitrogen element is arranged is method by chemical modification at carbon material surface, adds the functional group of containing the nitrogen element or carry out nitrating to passing into the compound that contains the nitrogen element in material with carbon element;
The method of described chemical modification is for by material with carbon element being impregnated in the liquid that ammoniacal liquor, nitric acid, pyridine or azodiisobutyronitrile contain the nitrogen element, with the method for post-drying, realizes that carbon material surface modifies the nitrogen element; The described functional group of containing the nitrogen element is a kind of of pyridine, pyrroles, quaternary nitrogen, nitro, amino or cyano group or more than one.
Describedly to passing into the compound that contains the nitrogen element in material with carbon element, carry out nitrating for pass into the presoma that ammonia, acetonitrile or pyridine contain the nitrogen element when the synthetic material with carbon element simultaneously, or the method that at high temperature to existing material with carbon element, passes into Nitrogen element gas is introduced nitrogen-atoms.
Preferably, described catalyst is one or more the nitrogen-doped carbon material in gold-supported, copper, bismuth, manganese or potassium, described gold, copper, bismuth, manganese or potassium exist with the form of chloride salt and rhodanate, wherein the mass fraction of gold is 0.05-0.3%, and the mass fraction of copper, bismuth, manganese or potassium is respectively 0.05-10.0%.
Preferably, described copper exists with the form of chlorate and rhodanate, and the mass fraction of copper is 0.05-10.0%.
Preferably, CNT, mesoporous carbon, Graphene or active carbon that described catalyst is is 0.1-20.0% nitrogen element doped with molar content, load has the gold of mass fraction 0.05-0.3% or the copper of 0.05-10.0%, and gold or copper exist with one or both forms of chloride or rhodanide.
Preferably, CNT, mesoporous carbon, Graphene or active carbon that described catalyst is is 0.1-10.0% nitrogen element doped with molar content, load has the gold of 0.05-0.3% or the copper of 0.05-5.0%, with one or both forms of chloride or rhodanide, exists.
The present invention compared with prior art, have the following advantages and the high-lighting effect: after the carbon carriers such as active carbon, CNT, mesoporous carbon and Graphene are carried out to the nitrogen doping, can effectively strengthen the dispersion of active component at carrier surface, promote the absorption on the active component surface and the reaction of acetylene and hydrogen chloride, catalytic activity can significantly improve; Under the same terms, without the nitrogen of Metal Supported doping carrier and thereon the catalyst activity effect of carried metal all be better than the catalyst of the same type of common carbon carrier and load.Gold, copper, bismuth or potassium etc. are as the reactive metal of catalyst, with the form of simple substance, chloride or rhodanide, are carried on the nitrating carbon carrier, green non-poisonous, active good, not volatile under reaction condition---and this invention is for the HgCl replaced in chlor-alkali industry
2catalyst has positive meaning.Surface or body be the interior carbon carrier doped with the nitrogen element mutually, the catalyst that gold-supported, copper, bismuth, manganese or potassium isoreactivity metal form, there is the catalyst prepared than common carbon carrier and there is higher acetylene hydrochlorination catalytic activity and lower deactivation rate, and the pollution of having avoided heavy metal and compound thereof to run off and bring, have more the characteristic of environmental protection.
Remarkable result of the present invention is can improve by the chemical modification to the carrier cheapness activity of same type catalyst, thereby can, by the cost of catalyst, more be close to industrialization; Except nitrogen-dopped activated carbon, introduce New Type of Carbon carrier nitrogen-doped carbon nanometer pipe, the doped meso-porous carbon of nitrogen and nitrogen-doped graphene, greatly promoted technological innovation and the improvement of acetylene hydrochlorination.
The accompanying drawing explanation
Fig. 1. example one is to the conversion ratio of example three curve over time.
Fig. 2. example five is to the conversion ratio of example nine catalyst curve over time.
Fig. 3. the conversion ratio of example ten and example 11 catalyst is curve over time.
Fig. 4. example 12 is to the conversion ratio of example 14 catalyst curve over time.
Fig. 5. the conversion ratio of example 15 catalyst is curve over time.
Fig. 6. the conversion ratio of example 16 catalyst is curve over time.
Fig. 7. the conversion ratio of example 17 catalyst is curve over time.
Fig. 8. example 18 is to the conversion ratio of example 21 catalyst curve over time.
Fig. 9. example 22 is to the conversion ratio of example 25 catalyst curve over time.
The specific embodiment
Below by instantiation, feature of the present invention and remarkable result are described.Wherein example one to four is for take the catalyst that nitrogen-dopped activated carbon is carrier, example five to nine is to take the catalyst that nitrogen-doped carbon nanometer pipe is carrier, example ten to 11 is to take the catalyst that nitrogen-doped graphene is carrier, example 12 to 14 is catalyst carbon nano-tube modified without the nitrogen of Metal Supported, example 15 to 17 is respectively the catalyst of nitrogen-dopped activated carbon, nitrogen-doped graphene and the doped meso-porous carbon of nitrogen without Metal Supported, and example 18 to 25 is case of comparative examples.
Instantiation one: the Au catalyst of 0.35 wt% of nitrogen-dopped activated carbon load.Get the common coconut husk charcoal of 10g, by deionized water, clean impurity, its concrete steps are: get under 100ml deionized water normal temperature and soak the coconut husk charcoal 24 hours, filter afterwards; So repeat 3 times.Then active carbon is positioned over to 120
the drying in oven of C 10 hours.Under the condition of the isolated air of 600 oC, pass into the ammonia of 50ml/min and the hydrogen of 10ml/min (Beijing North wet body, high-purity, >=99.99%) after 5 hours, be down to gradually room temperature, close subsequently ammonia (the green water chestnut gas in Beijing, high-purity, >=99.99%) and hydrogen, now the nitrogen content of activated carbon bodies phase can bring up to 1.80% from 0.25%.Get 0.035g gold chloride (HAuCl
4h
2o, Acros,>=99.9%) be dissolved in the 8.5g deionized water, add 5g nitrogen doping coconut husk charcoal under the condition of stirring at room, stir after 2 hours and put into 130
the drying in oven of C 8 hours.
The appreciation condition of catalyst is: get the 0.3g catalyst, put into the nitrogen that U-shaped quartz ampoule passes into 10ml/min (Beijing North wet body, high-purity,>=99.99%), quartz ampoule is heated to 180
c keeps, after 10 minutes, stopping passing into nitrogen.The acetylene (Beijing North wet body, high-purity,>=99.99%) and the hydrogen chloride (the green water chestnut gas in Beijing,>=99.9%) of 6.6ml/min that pass into 6ml/min are estimated, and now the acetylene volume space velocity of reaction is 600 h
-1, hydrogen chloride flow/acetylene flow=1.1:1.0.
The initial activity of catalyst, high activity and selectively as shown in table 1, curve is as shown in Figure 1 over time for conversion ratio.
Instantiation two: the Au catalyst of the 0.05wt% of nitrogen-dopped activated carbon load.Get the common coconut husk charcoal of 5g, by deionized water, clean impurity, its preparation process is identical with example one.Active carbon is positioned over to 120
the drying in oven of C, after 10 hours, adds the ammoniacal liquor 100ml of 10mol/L under 25 oC, stirs 24 hours.After filtration, active carbon is positioned in isolated air and 500
pass into 10ml/min hydrogen under the condition of C 8 hours, now the nitrogen content of activated carbon surface can bring up to 1.00% from 0.25%.In example two, the appreciation condition of catalyst is identical with example one, and the acetylene volume space velocity is 600 h
-1, hydrogen chloride flow/acetylene flow=1.1:1.0.
The initial activity of catalyst, high activity and selectively as shown in table 1, curve is as shown in Figure 1 over time for conversion ratio.
Instantiation three: the copper catalyst of the 5.0wt% of nitrogen-dopped activated carbon load.The nitrogen doping coconut husk charcoal that weighing 5g is identical with example one, get 0.68g copper chloride (CuCl
22H
2o, Beijing Chemical Plant, analyze pure) be dissolved in the 8.5g deionized water, add nitrogen-dopped activated carbon under the condition of stirring at room, stir after 2 hours and put into 130
the drying in oven of C 8 hours.In example three, the appreciation condition of catalyst is identical with example one, and the acetylene volume space velocity is 600 h
-1, hydrogen chloride flow/acetylene flow=1.1:1.0.
The initial activity of catalyst, high activity and selectively as shown in table 1, curve is as shown in Figure 1 over time for conversion ratio.
Instantiation four: the Mn catalyst of the 15.0wt% of nitrogen-dopped activated carbon load.The nitrogen doping coconut husk charcoal that weighing 5g is identical with example one, get 3.13g manganese chloride (MnCl
24H
2o, Beijing Chemical Plant, analyze pure) be dissolved in the 8.5g deionized water, add nitrogen-dopped activated carbon under the condition of stirring at room, stir after 2 hours and put into 130
the drying in oven of C 8 hours.In example three, the appreciation condition of catalyst is identical with example one, and the acetylene volume space velocity is 600 h
-1, hydrogen chloride flow/acetylene flow=1.1:1.0.
The initial activity of catalyst, high activity and selectively as shown in table 1, curve is as shown in Figure 1 over time for conversion ratio.
Instantiation five: the copper catalyst of 1.0 wt% of nitrogen-doped carbon nanometer pipe load.Get nitrogen-doped carbon nanometer pipe 1g prepared as Carbon and nitrogen sources respectively by ethene and ammonia, wherein nitrogen content is 8.0%.Get the 0.13g copper chloride and be dissolved in the 2g deionized water, under the condition of stirring at room, add nitrogen-doped carbon nanometer pipe, stir after 2 hours and put into 130
the drying in oven of C 8 hours.
The appreciation condition of catalyst is: get the 0.2g catalyst, put into the nitrogen that U-shaped quartz ampoule passes into 10ml/min, quartz ampoule is heated to 180
c keeps, after 10 minutes, stopping passing into nitrogen.Pass into the acetylene of 1.8ml/min and the hydrogen chloride of 1.98ml/min and estimated, now the acetylene volume space velocity of reaction is 180 h
-1, hydrogen chloride flow/acetylene flow=1.1:1.0.
The initial activity of catalyst, high activity and selectively as shown in table 2, curve is as shown in Figure 2 over time for conversion ratio.
Instantiation six: the Au catalyst of 0.25 wt% of nitrogen-doped carbon nanometer pipe load.Get nitrogen-doped carbon nanometer pipe 1g prepared as Carbon and nitrogen sources by ethene and acetonitrile, wherein nitrogen content is 4.0%.Get the 0.016g gold chloride and be dissolved in the 2g deionized water, under the condition of stirring at room, add nitrogen-doped carbon nanometer pipe, stir after 2 hours and put into 130
the drying in oven of C 8 hours.
The appreciation condition of catalyst is: get the 0.2g catalyst, put into the nitrogen of the logical 10ml/min of U-shaped quartz ampoule, quartz ampoule is heated to 180
c keeps, after 10 minutes, stopping passing into nitrogen.Pass into the acetylene of 6ml/min and the hydrogen chloride of 6.6ml/min and estimated, now the acetylene volume space velocity of reaction is 600h
-1, hydrogen chloride flow/acetylene flow=1.1:1.0.
The initial activity of catalyst, high activity and selectively as shown in table 2, curve is as shown in Figure 2 over time for conversion ratio.
Instantiation seven: the Au catalyst of 0.50 wt% of nitrogen-doped carbon nanometer pipe load.Get nitrogen-doped carbon nanometer pipe 1g prepared as Carbon and nitrogen sources by ethene and acetonitrile, wherein nitrogen content is 2.0%.Get the 0.016g gold chloride and be dissolved in the 2g deionized water, under the condition of stirring at room, add nitrogen-doped carbon nanometer pipe, stir the drying in oven 8 hours of putting into 130 C after 2 hours.
The appreciation condition of catalyst is consistent with instantiation five, and the acetylene volume space velocity is 600h
-1, hydrogen chloride flow/acetylene flow=1.1:1.0.
The initial activity of catalyst, high activity and selectively as shown in table 2, curve is as shown in Figure 2 over time for conversion ratio.
Instantiation eight: the catalyst of 0.2 wt% gold of nitrogen-doped carbon nanometer pipe load, 0.5wt% copper, 1.0 wt% potassium.Get the nitrogen-doped carbon nanometer pipe 5g that in example four, nitrogen content is 8%.Get the 0.02g gold chloride, the 0.133g copper chloride is dissolved in the 5g deionized water, weighing 0.124g potassium rhodanate (KSCN, Beijing Chemical Plant analyze pure) is dissolved in the 4g deionized water.Speed by potassium rhodanate solution with 0.2ml/min dropwise joins in gold chloride and copper chloride solution.After titration completes, under the condition of stirring at room, add nitrogen-doped carbon nanometer pipe, stir the drying in oven 8 hours of putting into 130 C after 2 hours.The appreciation condition of the catalyst of example seven is identical with example five, and the acetylene volume space velocity is 600h
-1, hydrogen chloride flow/acetylene flow=1.1:1.0.
The initial activity of catalyst, high activity and selectively as shown in table 2, curve is as shown in Figure 2 over time for conversion ratio.
Instantiation nine: the carbon nanotube loaded 10wt% bismuth catalyst that nitrogen-containing functional group is modified.Get the multi-walled carbon nano-tubes that 2g is common, spend hydrochloric acid and hydrofluoric acid and clean catalyst and dry under 120 C.Add wherein subsequently the 20g azodiisobutyronitrile (AIBN, analyze pure, Tianjin) and 50g absolute ethyl alcohol (C
2h
5oH, analyze pure, Beijing Chemical Plant), stir suction filtration after 5 hours under 60oC, and, with 100g absolute ethanol washing 3 times, then dry under 120 C.It is 2% that the method can obtain nitrogen content, and finishing has the CNT of the nitrogen-containing functional groups such as cyano group.Weighing 0.03g bismuth chloride (BiCl
3, Beijing Chemical Plant, analyze pure) be dissolved in the 2g deionized water, the CNT after getting 1g and modifying is added to bismuth chloride solution, and 25 C stir the drying in oven 8 hours of putting into 130 C after 2 hours.The appreciation condition of the catalyst of example eight is identical with example five, and the acetylene volume space velocity is 600h
-1, hydrogen chloride flow/acetylene flow=1.1:1.0.
The initial activity of catalyst, high activity and selectively as shown in table 2, curve is as shown in Figure 2 over time for conversion ratio.
Instantiation ten: the 0.5wt% Au catalyst of nitrogen-doped graphene load.Get the 10g graphite oxide and mix with the ratio of 1 mg/mL with deionized water, clear without particulate material to solution by supersonic oscillations, add appropriate hydrazine hydrate (N
2h
4h
2o, analyze pure, Beijing Chemical Plant) at 100 C backflow 24h, produce the black particle shape precipitation, filter, dry, can obtain Graphene.Get the 2g Graphene under the condition of the isolated air of 600 oC, pass into the hydrogen of the ammonia of 50ml/min and 10ml/min after 5 hours, be down to gradually room temperature, close subsequently ammonia and hydrogen, now the nitrogen content of nitrogen-doped graphene body phase can bring up to 4.0%.Get 0.01g gold chloride (HAuCl
4h
2o, Acros,>=99.9%) be dissolved in the 2.0g deionized water, add the 1g nitrogen-doped graphene under the condition of stirring at room, stir after 2 hours and put into 130
the drying in oven of C 8 hours.
The appreciation condition of catalyst is: get the 0.22g catalyst, put into the nitrogen that U-shaped quartz ampoule passes into 10ml/min, quartz ampoule is heated to 180
c keeps, after 10 minutes, stopping passing into nitrogen.Pass into the acetylene of 6.0ml/min and the hydrogen chloride of 6.6ml/min and estimated, now the acetylene volume space velocity of reaction is 600 h
-1, hydrogen chloride flow/acetylene flow=1.1:1.0.
The initial activity of catalyst, high activity and selectively as shown in table 3, curve is as shown in Figure 3 over time for conversion ratio.
Instantiation 11: the 2wt% potassium catalyst of nitrogen-doped graphene load.Get the Graphene that 5g is common, under the condition of the isolated air of 600oC, pass into the ammonia of 20ml/min and the hydrogen of 10ml/min (Beijing North wet body, high-purity, >=99.99%), after 5 hours, be down to gradually room temperature, close subsequently ammonia (the green water chestnut gas in Beijing, high-purity, >=99.99%) and hydrogen, now the nitrogen content of activated carbon bodies phase can bring up to 3.5%.Get the 0.1g potassium rhodanide and be dissolved in the 4.2g deionized water, add 2g nitrogen doping nitrogen-doped graphene under the condition of stirring at room, stir after 2 hours and put into 130
the drying in oven of C 8 hours.
The appreciation condition of catalyst is: get the 0.22g catalyst, put into the nitrogen that U-shaped quartz ampoule passes into 10ml/min, quartz ampoule is heated to 180
c keeps, after 10 minutes, stopping passing into nitrogen.Pass into the acetylene of 3.6ml/min and the hydrogen chloride of 3.96ml/min and estimated, now the acetylene volume space velocity of reaction is 360 h
-1, hydrogen chloride flow/acetylene flow=1.1:1.0.
The initial activity of catalyst, high activity and selectively as shown in table 3, curve is as shown in Figure 3 over time for conversion ratio.
Instantiation 12: nitrogen-doped carbon nanometer pipe catalyst.Get and using nitrogen-doped carbon nanometer pipe 1g prepared as Carbon and nitrogen sources respectively by ethene and ammonia, wherein nitrogen content is 4.4%, 130
c is placed down in drying in oven 8 hours.The appreciation condition of catalyst is consistent with example four, and now the acetylene volume space velocity of reaction is 180 h
-1, hydrogen chloride flow/acetylene flow=1.1:1.0.
The initial activity of catalyst, high activity and selectively as shown in table 4, curve is as shown in Figure 4 over time for conversion ratio.
Instantiation 13: nitrogen-doped carbon nanometer pipe catalyst.Get and using nitrogen-doped carbon nanometer pipe 1g prepared as Carbon and nitrogen sources by ethene and acetonitrile, wherein nitrogen content is 7.8%, 130
c is placed down in drying in oven 8 hours.The appreciation condition of catalyst is consistent with example four, and now the acetylene volume space velocity of reaction is 180 h
-1, hydrogen chloride flow/acetylene flow=1.1:1.0.
The initial activity of catalyst, high activity and selectively as shown in table 4, curve is as shown in Figure 4 over time for conversion ratio.
Instantiation 14: the carbon nano-tube catalyst of nitrogen functional group's finishing.Get the CNT 1g that the finishing of processing with instantiation eight same procedure has cyano group, wherein nitrogen content is 1.4%.130
c is placed down in drying in oven 8 hours.The appreciation condition of catalyst is consistent with example four, and now the acetylene volume space velocity of reaction is 180 h
-1, hydrogen chloride flow/acetylene flow=1.1:1.0.
The initial activity of catalyst, high activity and selectively as shown in table 4, curve is as shown in Figure 4 over time for conversion ratio.
Instantiation 15: nitrogen-dopped activated carbon catalyst.Get the nitrogen-dopped activated carbon 1g processed with instantiation one same procedure, wherein nitrogen content is 1.80%.130
c is placed down in drying in oven 8 hours.
The appreciation condition of catalyst is: get the 0.5g catalyst, put into the nitrogen that U-shaped quartz ampoule passes into 10ml/min (Beijing North wet body, high-purity,>=99.99%), quartz ampoule is heated to 180
c keeps, after 10 minutes, stopping passing into nitrogen.The acetylene (Beijing North wet body, high-purity,>=99.99%) and the hydrogen chloride (the green water chestnut gas in Beijing,>=99.9%) of 6.6ml/min that pass into 6ml/min are estimated, and now the acetylene volume space velocity of reaction is 360 h
-1, hydrogen chloride flow/acetylene flow=1.1:1.0.
The initial activity of catalyst, high activity and selectively as shown in table 5, curve is as shown in Figure 5 over time for conversion ratio.
Instantiation 16: nitrogen-doped graphene catalyst.Get the nitrogen-doped graphene 1g processed with instantiation nine same procedure, wherein nitrogen content is 4.0%.130
c is placed down in drying in oven 8 hours.The appreciation condition of catalyst is consistent with example nine, and now the acetylene volume space velocity of reaction is 600 h
-1, hydrogen chloride flow/acetylene flow=1.1:1.0.
The initial activity of catalyst, high activity and selectively as shown in table 6, curve is as shown in Figure 6 over time for conversion ratio.
Instantiation 17: the doped meso-porous C catalyst of nitrogen.Get and using the doped meso-porous carbon 1g of nitrogen prepared as Carbon and nitrogen sources by methane and pyridine, wherein nitrogen content is 12.4%, 130
c is placed down in drying in oven 8 hours.
The appreciation condition of catalyst is: get the 0.18g catalyst, put into the nitrogen that U-shaped quartz ampoule passes into 10ml/min (Beijing North wet body, high-purity,>=99.99%), quartz ampoule is heated to 180
c keeps, after 10 minutes, stopping passing into nitrogen.The acetylene (Beijing North wet body, high-purity,>=99.99%) and the hydrogen chloride (the green water chestnut gas in Beijing,>=99.9%) of 3.96ml/min that pass into 3.6ml/min are estimated, and now the acetylene volume space velocity of reaction is 360 h
-1, hydrogen chloride flow/acetylene flow=1.1:1.0.
The initial activity of catalyst, high activity and selectively as shown in table 7, curve is as shown in Figure 7 over time for conversion ratio.
Instantiation 18: the Au catalyst of 0.25 activated carbon supported wt%.Get 0.035g gold chloride (HAuCl
4h
2o, Acros,>=99.9%) be dissolved in the 8.5g deionized water, add 5g coconut husk charcoal under the condition of stirring at room, stir after 2 hours and put into 130
the drying in oven of C 8 hours.
The appreciation condition of catalyst is consistent with the condition of example one, and now the acetylene volume space velocity of reaction is 600 h
-1, hydrogen chloride flow/acetylene flow=1.1:1.0.
The initial activity of catalyst, high activity and selectively as shown in table 8, curve is as shown in Figure 8 over time for conversion ratio.
Instantiation 19: the Mn catalyst of 15 activated carbon supported wt%.The coconut husk charcoal that weighing 5g is common, get 3.13g manganese chloride (MnCl
24H
2o, Beijing Chemical Plant, analyze pure) be dissolved in the 8.5g deionized water, add nitrogen-dopped activated carbon under the condition of stirring at room, stir after 2 hours and put into 130
the drying in oven of C 8 hours.In example three, the appreciation condition of catalyst is identical with example one, and the acetylene volume space velocity is 600 h
-1, hydrogen chloride flow/acetylene flow=1.1:1.0.
The initial activity of catalyst, high activity and selectively as shown in table 8, curve is as shown in Figure 8 over time for conversion ratio.
Instantiation 20: the copper catalyst of 5 carbon nanotube loaded wt%.Get the multi-walled carbon nano-tubes 1g prepared with example four same catalyst.Get the 0.13g copper chloride and be dissolved in the 2g deionized water, under the condition of stirring at room, add CNT, stir after 2 hours and put into 130
the drying in oven of C 8 hours.
The appreciation condition of catalyst is consistent with example four, and now the acetylene volume space velocity of reaction is 180 h
-1, hydrogen chloride flow/acetylene flow=1.1:1.0.
The initial activity of catalyst, high activity and selectively as shown in table 8, curve is as shown in Figure 8 over time for conversion ratio.
Instantiation 21: the potassium catalyst of 2 graphene-supported wt%.Get with instantiation ten in the common graphite alkene 2g of same raw materials, wherein do not detected the nitrogen element.Get the 0.1g potassium rhodanide and be dissolved in the 4.2g deionized water, add 2g nitrogen doping nitrogen-doped graphene under the condition of stirring at room, stir after 2 hours and put into 130
the drying in oven of C 8 hours., add nitrogen-doped carbon nanometer pipe under the condition of stirring at room, stir after 2 hours and put into 130
the drying in oven of C 8 hours.
The appreciation condition of catalyst is consistent with example four, and now the acetylene volume space velocity of reaction is 360 h
-1, hydrogen chloride flow/acetylene flow=1.1:1.0.
The initial activity of catalyst, high activity and selectively as shown in table 8, curve is as shown in Figure 8 over time for conversion ratio.
Instantiation 22: carbon nano-tube catalyst.Get the common multi-walled carbon nano-tubes 1g adulterated with not nitrogen identical in instantiation eight, do not contain the nitrogen element, 130
c is placed down in drying in oven 8 hours.The appreciation condition of catalyst is consistent with example four, and now the acetylene volume space velocity of reaction is 180 h
-1, hydrogen chloride flow/acetylene flow=1.1:1.0.
The initial activity of catalyst, high activity and selectively as shown in table 9, curve is as shown in Figure 9 over time for conversion ratio.
Instantiation 23: activated-carbon catalyst.Get untreated common active carbon 1g identical with instantiation one.130
c is placed down in drying in oven 8 hours.
The appreciation condition of catalyst is identical with instantiation 14.Now the acetylene volume space velocity of reaction is 360 h
-1, hydrogen chloride flow/acetylene flow=1.1:1.0.
The initial activity of catalyst, high activity and selectively as shown in table 9, curve is as shown in Figure 9 over time for conversion ratio.
Instantiation 24: graphen catalyst.Get the common graphite alkene 1g of the not nitrogen doping of processing with instantiation nine same procedure.130
c is placed down in drying in oven 8 hours.The appreciation condition of catalyst is consistent with example nine, and now the acetylene volume space velocity of reaction is 600 h
-1, hydrogen chloride flow/acetylene flow=1.1:1.0.
The initial activity of catalyst, high activity and selectively as shown in table 9, curve is as shown in Figure 9 over time for conversion ratio.
Instantiation 25: gold/mesoporous carbon catalyst.Get and take mesoporous carbon 1g prepared as carbon source by methane.130
c is placed down in drying in oven 8 hours.The appreciation condition of catalyst is consistent with example 17, and now the acetylene volume space velocity of reaction is 360 h
-1, hydrogen chloride flow/acetylene flow=1.1:1.0.
The initial activity of catalyst, high activity and selectively as shown in table 9, curve is as shown in Figure 9 over time for conversion ratio.
Above-mentioned instantiation shows that the catalyst of apply for protection has following feature: described catalyst formulation does not contain the toxic metals elements such as mercury, can effectively avoid heavy metal pollution; Described catalyst carrier is the carbon carrier that nitrogen doping chemical modification is carried out on body phase or surface, comprises active carbon, CNT and Graphene, and its synthetic catalyst activity is better than catalyst prepared by general carrier; The easy green of described catalyst carrier preparation method, be applicable to industrial applications; In described catalyst formulation, gold loading is equal to or less than the gold loading of existing bibliographical information.Described catalyst formulation has good catalytic activity and stability under described reaction condition, and catalysqt deactivation is not obvious.
Table 1 example one is to the initial activity of example four catalyst, high activity and selective
Table 2 example five is to the initial activity of example nine catalyst, high activity and selective
The initial activity of table 3 example ten and example 11 catalyst, high activity and selective
Table 4 example 12 is to the initial activity of example 14 catalyst, high activity and selective
The initial activity of table 5 example 15 catalyst, high activity and selective
The initial activity of table 6 example 16 catalyst, high activity and selective
The initial activity of table 7 example 17 catalyst, high activity and selective
Table 8 example 18 is to the initial activity of example 21 catalyst, high activity and selective
Table 9 example 22 is to the initial activity of example 25 catalyst, high activity and selective
Claims (11)
1. the catalyst of a nitrogen-doped carbon material load is characterized in that: described catalyst is one or more the nitrogen-doped carbon material without in Metal Supported or gold-supported, copper, bismuth, manganese or potassium; Described nitrogen-doped carbon material is carbon material surface or bulk phase-doped the nitrogen element is arranged.
2. catalyst according to claim 1, it is characterized in that: in described nitrogen-doped carbon material, the molar content of nitrogen element is 0.1-20.0%.
3. catalyst according to claim 1, it is characterized in that: the mass fraction of described gold in catalyst is 0.05-0.3%; Described copper, bismuth, manganese, the potassium mass fraction in catalyst is respectively 0.05-15.0%; Described gold, copper, bismuth, manganese, potassium exist with one or more states in metal simple-substance, chloride, rhodanide or cyanide.
4. catalyst according to claim 1 is characterized in that: described nitrogen-doped carbon material is a kind of in active carbon, CNT, mesoporous carbon, Graphene or more than one.
5. catalyst according to claim 1 is characterized in that: described surface or bulk phase-doped the nitrogen element is arranged is method by chemical modification at carbon material surface, adds the functional group of containing the nitrogen element or carry out nitrating to passing into the compound that contains the nitrogen element in material with carbon element.
6. catalyst according to claim 7, it is characterized in that: the method for described chemical modification is for by material with carbon element being impregnated in the liquid that ammoniacal liquor, nitric acid, pyridine or azodiisobutyronitrile contain the nitrogen element, with the method for post-drying, realizes that carbon material surface modifies the nitrogen element; The described functional group of containing the nitrogen element is a kind of of pyridine, pyrroles, quaternary nitrogen, nitro, amino or cyano group or more than one.
7. catalyst according to claim 7, it is characterized in that: describedly to passing into the compound that contains the nitrogen element in material with carbon element, carry out nitrating for pass into the presoma that ammonia, acetonitrile or pyridine contain the nitrogen element when the synthetic material with carbon element simultaneously, or the method that at high temperature to existing material with carbon element, passes into Nitrogen element gas is introduced nitrogen-atoms.
8. catalyst according to claim 1, it is characterized in that: described catalyst is one or more the nitrogen-doped carbon material in gold-supported, copper, bismuth, manganese or potassium, described gold, copper, bismuth, manganese or potassium exist with the form of chloride salt and rhodanate, wherein the mass fraction of gold is 0.05-0.3%, and the mass fraction of copper, bismuth, manganese or potassium is respectively 0.05-10.0%.
9. catalyst according to claim 1, it is characterized in that: described copper exists with the form of chlorate and rhodanate, and the mass fraction of copper is 0.05-10.0%.
10. catalyst according to claim 1, it is characterized in that: CNT, mesoporous carbon, Graphene or active carbon that described catalyst is is 0.1-20.0% nitrogen element doped with molar content, load has the gold of mass fraction 0.05-0.3% or the copper of 0.05-10.0%, and gold or copper exist with one or both forms of chloride or rhodanide.
11. catalyst according to claim 1, it is characterized in that: CNT, mesoporous carbon, Graphene or active carbon that described catalyst is is 0.1-10.0% nitrogen element doped with molar content, load has the gold of 0.05-0.3% or the copper of 0.05-5.0%, with one or both forms of chloride or rhodanide, exists.
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