CN103846101B - A kind of C-SiC catalyst and Synthesis and applications thereof - Google Patents

A kind of C-SiC catalyst and Synthesis and applications thereof Download PDF

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CN103846101B
CN103846101B CN201210496796.5A CN201210496796A CN103846101B CN 103846101 B CN103846101 B CN 103846101B CN 201210496796 A CN201210496796 A CN 201210496796A CN 103846101 B CN103846101 B CN 103846101B
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CN103846101A (en
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包信和
李星运
潘秀莲
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Dalian Institute of Chemical Physics of CAS
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Abstract

The invention discloses a kind of Novel non-metal catalyst and the Synthesis and applications thereof of preparing vinyl chloride for acetylene method.This catalyst is SiC based composites, by controlling growth conditions and post-treatment condition, SiC grows the C layer of skim different-shape and chemical composition, directly catalyzing acetylene and hcl reaction can generate vinyl chloride, and it is selective to show higher activity, stability and vinyl chloride.Advantage of the present invention achieves acetylene method to prepare the nonmetal catalyzed of vinyl chloride, solves the high pollution problem of the mercuric chleride catalyst of current industrial use, and avoid using noble metal even metallic catalyst, has higher environmental benefit and economic worth.

Description

A kind of C-SiC catalyst and Synthesis and applications thereof
Technical field
The present invention relates to the non-metallic catalyst preparing vinyl chloride for acetylene method: C-SiC composite and synthesis thereof and application.
Background technology
Polyvinyl chloride (PVC) is second-biggest-in-the-world thermoplastic resin, plays great effect in Chinese national economy and social development.Vinyl chloride is the important monomer producing PVC.Due to the present situation of the few oily lean gas of the many coals of China, the production ways mainly acetylene method of VC in China.Existing industrial preparing chloroethylene by acetylene hydrochlorination reaction is mainly the mercuric chleride catalyst of carrier with active carbon, but China's mercury scarcity of resources, and the distillation of mercuric chleride catalyst, the toxicity brought of running off and problem of environmental pollution also become the serious problems that long-standing problem acetylene method prepares process for vinyl chloride route.Therefore, the alternative of mercury catalyst is that China's acetylene method prepares problem demanding prompt solution in vinyl chloride industry.
In succession carry out the research of non-mercury catalyzing acetylene hydrochlorinate preparing chloroethylene in the world.Hutchings carries out contrast to the activity of a series of metal chloride and finds that the catalytic activity of catalyst corresponds to the standard electrode potential (JournalofCatalysis250 (2007) 231 – 239) of metal ion, Au 3+owing to having higher electrode potential (Eo is about 1.42V), show and be better than Hg 2+initial activity, be the catalyst being expected to replacement for mercury present stage.But gold ion is as the easy inactivation (POLYVINYLCHLORIDE (2009) 37-9) by reaction gas Acetylene Reduction in course of reaction during catalyst, so large quantity research concentrates on the modification to Au catalyst, to improve its stability.Wherein the Au-La-Co composite catalyst (patent No.: 201110199651.4) taking porous carbon as carrier has been prepared by Shihezi Univ and University Of Tianjin, conversion of alkyne can reach more than 90%, vinyl chloride is selective reaches more than 98.5%, life-span can reach more than 1000h, and after activating and regenerating, its performance can return to more than 90% of originality energy, is the non-mercury catalyst of current performance the best.But gold is as the noble metal catalyst of scarcity of resources, and it is expensive, and Au catalyst will use chloroazotic acid in preparation process, has larger corrosion and pollution problem.Therefore, exploitation non-mercury, non-precious metal catalyst, produce extremely urgent with the high-efficiency cleaning realizing PVC.
Porous carbon materials is often used as catalyst carrier, but recently large quantity research finds, material with carbon element inherently can as excellent catalyst, such as: Robert practical graphite, carbon fibers such as (Angew.Chem.Int.Ed.40 (2001) 2066) are directly used for vinylbenzene oxidative dehydrogenation as catalyst and prepare styrene, Su Dangsheng etc. (SCIENCE322 (2008) 73-76) study discovery, carbon pipe after functionalized directly has well active and selective as catalyst butane oxidation dehydrogenation reaction, Dai Lining etc. (NanoLett9 (2009) 2255-2259) find that Graphene catalytic activity in ORR reaction that N adulterates even is better than commodity Pt/C catalyst.
But prepare in vinyl chloride at acetylene method, the application of non-metallic catalyst has no report.
Summary of the invention
The object of the present invention is to provide a kind of non-metallic catalyst C-SiC composite and the Synthesis and applications thereof of preparing vinyl chloride for acetylene method.
A kind of for acetylene method prepare vinyl chloride non-metallic catalyst C-SiC composite composition and weighing scale comprise:
A) the shaping SiC skeleton of 30% ~ 90%;
B) the porous surface carbon-coating of 5% ~ 60%;
Or, doped with the atom N of 1% ~ 15% in carbon-coating structure;
Or, doped with the B atom of 1% ~ 10% in carbon-coating structure;
A kind of novel metalloid catalyst preparing and method of modifying preparing vinyl chloride for acetylene method:
A) preparation method of C-SiC material: SiC is elevated to 700-1000 DEG C by programme-control with 3-10 DEG C/min of heating rate under an inert atmosphere, then chloro-carbon solvent is passed into (after passing into chloro-carbon solvent by inert gas by bubbling inert gas form, again the inert gas carrying chloro-carbon solvent is introduced in the reaction system at SiC particle place under room temperature), reaction 0.1-5 hour, lowers the temperature under an inert atmosphere.Chloro-carbon solvent be carbon tetrachloride, chloroform, carrene, chlorine, hydrogen chloride chloro-carbon solvent one or two or more kinds.Inert atmosphere is the one in nitrogen, argon gas, helium.Flow 20 ~ 80 ml/min.
B) the surface nitrogen atom doping vario-property of C-SiC material: nitrogen-atoms can be mix after the process situ generating carbon-coating mixes or generates carbon-coating:
D) the original position nitrogen atom doping of C-SiC: in preparation C-SiC process, nitrogenous precursor is passed into while passing into chloro-carbon solvent, carry out situ Nitrogen Doping, nitrogenous precursor comprises: one or two or more kinds of ammonia, acetonitrile, hydrazine, and the volume ratio of nitrogenous precursor and chloro-carbon solvent is 1:5 ~ 5:1.
E) C-SiC post processing nitrogen atom doping: C-SiC synthesize after at 500 DEG C ~ 1200 DEG C, through reacting nitrating with nitrogenous precursor, nitrogenous precursor comprises: one or two or more kinds of ammonia, acetonitrile, hydrazine, nitrogen, nitrogenous precursor flow velocity is 20-500ml/min, reaction temperature is 600 DEG C ~ 1200 DEG C, and the reaction time is 2-12h.
F) the atom doped modification of the surface boron of C-SiC material: boron atom can be mix after the process situ generating carbon-coating mixes or generates carbon-coating:
G) in-situ boron of C-SiC is atom doped: in preparation C-SiC process, boracic precursor is passed into while passing into chloro-carbon solvent, carry out in-situ boron doping, boracic precursor comprises: the one of boron chloride, borine or two kinds, and the volume ratio of boracic precursor and chloro-carbon solvent is 1:5 ~ 15:1.
F) C-SiC post processing boron is atom doped: after C-SiC synthesis through with boracic precursor mechanical mixture after react at 500 DEG C ~ 1200 DEG C and carry out boron doping, boracic precursor comprises: one or two or more kinds of boron chloride, borine, boron oxide, boric acid, the mass ratio of boracic precursor and chloro-carbon solvent is 1:100 ~ 200:1, and the reaction time is 2-20h.
G) C-SiC ball-milling treatment modification: put into ball grinder after being mixed with stainless steel steel ball by C-SiC and carry out ball milling, C-SiC and steel ball quality are than being 1:8-1:36, and steel ball size is 1-5cm rotating speed is 200-600 rev/min, and Ball-milling Time is 3-30h.
The invention provides a kind of nonmetal its advantage of C-SiC composite catalyst preparing vinyl chloride for acetylene method is:
1. raw material is cheaply easy to get, and can utilize shaping SiC precursor one-step synthesis integral catalyzer, be applicable to commercial Application;
2. synthesis condition is easily controlled, and can form the C-SiC composite of different structure by changing the conditions such as reaction temperature, reaction time, reaction atmosphere composition, ball milling parameter.
3. the C-SiC catalyst through modification shows higher catalytic activity, vinyl chloride is selective, and stable reaction performance, be expected to replace metallic catalyst, realize without mercury catalytic process, greatly reduce acetylene method and prepare vinyl chloride production cost, and avoid the pollution problem of mercury catalyst, there is important economic worth and social effect.
Accompanying drawing explanation
The Raman of Fig. 1 .C-SiC composite characterizes;
The N of Fig. 2 .C-SiC composite 2adsorption desorption curve;
The XPS spectrum figure of the C-SiC composite that Fig. 3 .B adulterates;
The XPS spectrum figure of the C-SiC composite that Fig. 4 .N adulterates
The active comparison diagram of VCM synthesis of Fig. 5 .C-SiC, B-C-SiC, N-C-SiC;
Fig. 6. the catalytic activity of the N-C-SiC under different air speed.
Detailed description of the invention
Below by embodiment, whole process is described in further detail, but right of the present invention is not by the restriction of these embodiments.Meanwhile, embodiment just gives and realizes this object partial condition, but and does not mean that must meet these conditions just can reach this object.
Embodiment 1
0.80gSiC particle (40-60 order) is put into tube furnace, passing into temperature programming to 800 DEG C under Ar gas atmosphere, heating rate is 5 DEG C/min, then CCl4 liquid is passed into by Ar gas bell form, Ar flow velocity is 50ml/min, the time of passing into is respectively 2h, then switches to pure Ar atmosphere borehole cooling.Obtained sample called after C-SiC.
Fig. 1 is that the Raman of obtained sample characterizes, and shows the characteristic peak of carbon-coating: D peak and G peak, prove the generation of carbon-coating in Raman figure.
Fig. 2 is the adsorption desorption curve map of obtained C-SiC sample, and its specific area is 181m 2/ g, proves that the carbon-coating generated is porous carbon layer.
Embodiment 2
The preparation of boron doped B-C-SiC material: by 1.2gC-SiC and B 2o 3mechanical mixture, B 2o 3be 1:3 with the mass ratio of C-SiC, be placed in high temperature furnace, under Ar gas atmosphere, rise to 1100 ° of C with the programming rate of 5 ° of C/min, insulation 6h, after cooling, the NaOH solution of taking-up 30wt% is fully washed, suction filtration, dries under 120 ° of C, obtained sample called after B-C-SiC.Fig. 3 is the XPS spectrum figure of B-C-SiC, proves that B atom is successfully doped into carbon-coating skeleton, and it is 1.3% that B atom accounts for carbon-coating mass ratio.
Embodiment 3
The preparation of the N-C-SiC material of N doping: 0.80gSiC particle (40-60 order) puts into tube furnace, passing into temperature programming to 800 DEG C under Ar gas atmosphere, heating rate is 5 DEG C/min, then by CCl 4liquid is passed into by Ar gas bell form, and Ar flow velocity is 50ml/min, and while passing into CCl4, NH3 is passed into by an other road simultaneously, NH 3flow velocity is 9ml/min, continues to pass into 2h, then switches to pure He atmosphere borehole cooling, obtained sample called after N-C-SiC.Fig. 4 is the XPS spectrum figure of N-C-SiC, and atom N is successfully adulterated as carbon-coating skeleton as seen from Figure 4, and it is 9.6% that atom N accounts for carbon-coating mass ratio.
Embodiment 4
Installed to by catalyst in fixed bed reactors, reaction temperature is 200 ° of C, and air speed is 177h -1, acetylene and vinyl chloride volume ratio are 1.15:1.The reactivity figure that Fig. 5 is C-SiC, B-C-SiC, NC-SiC under as above reaction condition, as seen from the figure, the doping of B, N can significantly improve reactivity, and wherein the doping of N is the most obvious to the promotion of reactivity.
Embodiment 5
Install in fixed bed reactors by N-C-SiC sample, reaction temperature is 200 ° of C, and acetylene and vinyl chloride volume ratio are 1.15:1, changes reaction velocity, respectively 289h -1, 177h -1, 95h -1, 40.3h -1lower its reactivity of investigation.As shown in Figure 6, N-C-SiC reactivity improves with the reduction of air speed result, wherein at 40.3h -1under air speed, N-C-SiC illustrates high activity: conversion of alkyne is 84%, selective >99%.And reaction 50h non-inactivation, there is good reaction stability.
N-C-SiC has high activity and high stable, and N-C-SiC combines the premium properties of SiC substrate: high mechanical properties and easy-formation performance.So it has fabulous prospects for commercial application as catalyst.

Claims (7)

1. a C-SiC catalyst, it is the SiC particle that surface has porous carbon layer, it is characterized in that:
A) SiC: be the 5-500 object SiC particle of α phase and/or beta phase structure;
B) porous carbon layer of SiC particle surface, can account for 5% ~ 60% of whole catalyst weight;
Doped with atom N in described porous carbon layer structure, the doping of atom N is 1% ~ 15% of porous carbon layer quality;
Or doped with B atom in described porous carbon layer structure, the doping of B atom is 1% ~ 10% of porous carbon layer quality.
2. catalyst as claimed in claim 1, is characterized in that:
Described carborundum is α phase, β phase or both mixed phases, and granularity is 5-100 order, specific area 1-200m 2the porous, shaped carborundum of/g, foam silicon carbon or SiC powder.
3. a preparation method for C-SiC catalyst described in claim 1, is characterized in that: preparation method is:
A) preparation method of C-SiC material: SiC particle is heated up from room temperature to 700-1000 DEG C by programme-control under an inert atmosphere, then chloro-carbon solvent is passed into by bubbling inert gas form, after passing into chloro-carbon solvent by inert gas, again the inert gas carrying chloro-carbon solvent is introduced in the reaction system at SiC particle place under room temperature, reaction 0.1-5 hour, be cooled to room temperature under an inert atmosphere, form porous carbon layer in SiC particle surface; Obtain C-SiC catalyst; Heating rate is 3-10 DEG C/min;
The surface nitrogen atom doping vario-property of C-SiC material: nitrogen-atoms mixes after the process situ generating carbon-coating mixes or generates carbon-coating;
Original position nitrating: in preparation C-SiC process, in reaction system, nitrogenous precursor is passed into while passing into chloro-carbon solvent, carry out situ Nitrogen Doping, nitrogenous precursor comprises: one or two or more kinds in ammonia, acetonitrile, hydrazine, the volume ratio of nitrogenous precursor and chloro-carbon solvent is 1:5 ~ 5:1, and reaction temperature is 700-1000 DEG C; All the other conditions with above-mentioned steps a);
After C-SiC post processing nitrogen atom doping: C-SiC synthesizes at 500 DEG C ~ 1200 DEG C, pass into the reaction of nitrogenous precursor and carry out nitrating, nitrogenous precursor comprises: one or two or more kinds in ammonia, acetonitrile, hydrazine, nitrogen, nitrogenous precursor flow velocity is 20-500ml/min, reaction temperature is 600 DEG C ~ 1200 DEG C, and the reaction time is 2-12h;
Or, the atom doped modification of surface boron of C-SiC material: boron atom mixes after the process situ generating carbon-coating mixes or generates carbon-coating;
The in-situ boron of C-SiC is atom doped: in preparation C-SiC process, in reaction system, boracic precursor is passed into while passing into chloro-carbon solvent, carry out in-situ boron doping, boracic precursor comprises: one or two or more kinds in boron chloride, borine, the volume ratio of boracic precursor and chloro-carbon solvent is 1:5 ~ 15:1, and reaction temperature is 700-1000 DEG C; All the other conditions with above-mentioned steps a);
C-SiC post processing boron is atom doped: after C-SiC synthesis through with boracic precursor mechanical mixture after react at 500 DEG C ~ 1200 DEG C and carry out boron doping, boracic precursor comprises: one or two or more kinds in boron chloride, borine, boron oxide, boric acid, the mass ratio of boracic precursor and chloro-carbon solvent is 1:100 ~ 200:1, and the reaction time is 2-20h.
4. preparation method as claimed in claim 3, is characterized in that: further comprising the steps of:
C-SiC ball-milling treatment modification: put into ball grinder after C-SiC catalyst step a) obtained mixes with stainless steel steel ball and carry out ball milling, C-SiC and steel ball quality are than being 1:8 ~ 1:36, steel ball size is 1-5cm rotating speed is 200-600 rev/min, and Ball-milling Time is 3-30h; Obtain the C-SiC catalyst of ball milling modification.
5. the preparation method as described in claim 3 or 4, is characterized in that: described chloro-carbon solvent is one or two or more kinds in carbon tetrachloride, chloroform or carrene; Inert atmosphere is the one in nitrogen, argon gas, helium; Flow 20 ~ 80 ml/min.
6. the application of C-SiC catalyst described in a claim 1 or 2 in the reaction of acetylene method synthesizing chloroethylene.
7. apply as claimed in claim 6, it is characterized in that: C-SiC catalyst application is prepared in vinyl chloride in acetylene and hcl reaction, reaction temperature is 150-250 DEG C, and air speed is 5-1000h - 1, acetylene and hydrogen chloride volume ratio are 1:1 ~ 1:2.
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CN105618096A (en) * 2014-10-29 2016-06-01 中国科学院大连化学物理研究所 Fe-N-C/C-SiC catalyst and preparation and application thereof
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CN108246327B (en) * 2016-12-28 2020-11-10 南开大学 Preparation method and use method of nitrogen-doped carbon material catalyst for fixed bed acetylene hydrochlorination
CN110980736A (en) * 2019-11-15 2020-04-10 中国人民解放军陆军工程大学 Preparation method and application of silicon carbide-porous carbon one-dimensional nano wave-absorbing material
CN111229274B (en) * 2020-03-13 2022-08-19 浙江工业大学 High-energy mechanical ball-milling SiC Lewis acid catalyst and preparation method and application thereof

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