CN106902820A - A kind of synthesis of graphene-based catalyst of high concentration preparation of ethylene through selective hydrogenation of acetylene and application process - Google Patents
A kind of synthesis of graphene-based catalyst of high concentration preparation of ethylene through selective hydrogenation of acetylene and application process Download PDFInfo
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- CN106902820A CN106902820A CN201710109283.7A CN201710109283A CN106902820A CN 106902820 A CN106902820 A CN 106902820A CN 201710109283 A CN201710109283 A CN 201710109283A CN 106902820 A CN106902820 A CN 106902820A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
- B01J23/50—Silver
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
- C07C5/03—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of non-aromatic carbon-to-carbon double bonds
- C07C5/05—Partial hydrogenation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
- C07C2523/48—Silver or gold
- C07C2523/50—Silver
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
A kind of synthesis of graphene-based catalyst of high concentration preparation of ethylene through selective hydrogenation of acetylene and application process, it is Pd to use main active component in the graphite-based catalyst, helps active component for Ag, and with N-methyl pyrrolidones NMP as solvent, is synthesized under non-aqueous conditions.Catalyst proportion is palladium acetylacetonate:Silver acetate:Graphene:NMP=0.01~0.1g:0.05~0.5g:35g:0.1L, after dipping under the alkalescence condition of pH=9 12, is reduced by potassium borohydride to solid matter, you can obtain required catalyst.The catalyst is applied to during high concentration acetylene selective catalysis prepare ethylene reaction system, and wherein acetylene gas derives from carbide, and uses paste state bed reactor synthesizing ethylene under high-speed.In the present invention, catalyst have that conversion of alkyne is high, ethene selectivity is good, long lifespan the features such as.
Description
Technical field
The present invention relates to a kind of catalyst of high concentration selective catalytic hydrogenation of acetylene synthetic method and preparing ethene
During application, belong to catalyst preparation technical field.
Background technology
Ethene is most important basic material in petrochemical industry, and it is mainly derived from urging for oil or low-carbon paraffin at present
Change cracking.With petroleum resources increasingly depleted, in combination with China's energy characteristics rich in coal and poor in oil, calcium carbide is passed through by raw material of coal
Technique produces acetylene, then under selective hydrocatalyst effect, by Hydrogenation for ethylene product, can further expand coal
Chemical industry route.Calcium carbide production traditional handicraft energy consumption is higher, with technological progress, using the technology of heat accumulating type calcium carbide production new technique
So that the energy consumption of calcium carbide production, cost are greatly reduced so that preparation of ethylene through selective hydrogenation of acetylene has more preferable economic worth.
For acetylene hydrogenation research, developed mainly for the Catalytic Hydrogenation Techniques that a small amount of acetylene is removed in ethene at present, and to high concentration
The correlative study that selective catalytic hydrogenation of acetylene prepares ethene is relatively fewer.
The content of the invention
The first object of the present invention is to provide that a kind of conversion of alkyne is high, ethylene selectivity is good, solvent heat endurance is high
The graphene-based catalyst of high concentration producing ethylene with acetylene hydrogenation.
It is raw material that the second object of the present invention is to provide a kind of high concentration acetylene gas of utilization carbide generation, using slurry
Bed reactor, the ethylene reaction produced method of high concentration selective catalytic hydrogenation of acetylene is carried out using the first goal of the invention catalyst.
To realize the first goal of the invention, there is provided the graphene-based catalyst of such a, compared with prior art, it improves it
Place is that carrier is changed into Graphene, and with N-methyl pyrrolidones (NMP) as solvent, is synthesized under non-aqueous conditions.
It is and existing to realize the second goal of the invention, there is provided a kind of method that high concentration selective catalytic hydrogenation of acetylene prepares ethene
There is technology to compare, its improvements is that acetylene gas derives from carbide generator, with NMP as solvent, in paste state bed reactor,
By the catalyst action of the offer of the first mesh come synthesizing ethylene.
To realize the first and second purposes, it is comprised the following steps that：
Step (1)：By palladium acetylacetonate, silver acetate, Graphene, N-methyl pyrrolidones (NMP) according to a certain ratio anti-
Answer and carried out in kettle dipping composition mixed liquor；
Step (2)：The solid matter absolute ethanol washing suction filtration 2 that mixed liquor in step (1) is centrifugally separating to obtain
Dried after~3 times；
Step (3)：Potassium hydroxide and potassium borohydride deionized water are configured to alkaline solution, by consolidating in step (2)
Body material is persistently stirred at a certain temperature in adding alkaline solution, is then centrifugally separating to obtain catalyst.
Further, palladium acetylacetonate, silver acetate, Graphene, the proportioning of NMP are 0.01~0.1g in step (1):0.05
~0.5g:35g:0.1L.
Further, dipping method is carried out for 80~120 DEG C in temperature in step (1), and 6~12h is stirred under normal pressure.
Further, drying condition is maintenance 2~6 hours at 200~220 DEG C in step (2).
Further, stirring condition, to maintain 70~90 DEG C of temperature, continues mixing time 4~8 hours in step (3).
Further, the pH value of step (3) neutral and alkali solution is 9~12.
A kind of graphene-based catalyst prepared by the above method.
The invention also discloses the application process of above-mentioned graphene-based catalyst, comprise the following steps：
Step 1)：Graphene-based catalyst is added to the paste state bed reactor equipped with nmp solvent, by slurry reactor
Device bottom is passed through nitrogen bubble；
Step 2)：Air in solution is caught up with only by being passed through nitrogen, and is made in paste state bed reactor for nitrogen atmosphere condition
Under, the acetylene gas produced by carbide generator is introduced, it is passed directly into paste state bed reactor after acetylene gas is purified, acetylene volume
Concentration is more than 98.0%, while introducing hydrogen of the volumetric concentration more than 99.0%, gas is passed through in paste state bed reactor by bottom
And under uniform temperature and pressure successive reaction；
Step 3)：The gas-phase product of paste state bed reactor top outflow is collected, that is, obtains ethylene product.
Further, step 2) in, hydrogen and acetylene molar ratio are 4~8:1, operation air speed is 30000ml/ (g-cat
H), uniform temperature is 120~150 DEG C, and pressure is normal pressure.
As can be seen that the present invention is among traditional catalyst activity component from the scheme of the first goal of the invention is realized,
New carrier material is employed, catalyst has been synthesized in nonaqueous solvents, while being reduced by potassium borohydride alkaline solution so that
Catalyst achieves that reduction at normal temperatures, rather than as traditional catalyst, it is necessary to can just make after fixed bed high-temperature hydrogen reduction
With.Catalyst of the invention is easy to use, and meta-alkalescence, can reduce acetylene polymerization, improves the selectivity of ethene.According to realizing
The step of two goals of the invention carrys out selective catalysis and prepares the experimental verification of ethene to show, Pd the and Ag catalyst of Graphene matrix,
In paste state bed reactor under NMP reaction atmospheres, can disperse active component more uniform, solvent heat endurance is stronger, urges
Agent activity is improved, it is suppressed that the generation of high polymer, further increases the conversion ratio and selectivity of ethene.
With reference to specific embodiment, the present invention is further illustrated.
Brief description of the drawings
Fig. 1 is the synthesis step of the graphene-based catalyst of high concentration preparation of ethylene through selective hydrogenation of acetylene.
Specific embodiment
Following examples are used to illustrate the present invention, but are not limited to the scope of the present invention.
Embodiment 1
A kind of graphene-based catalyst of high concentration preparation of ethylene through selective hydrogenation of acetylene, its active component is Pd and Ag, its load
Body is Graphene, and with N-methyl pyrrolidones (NMP) as solvent, is synthesized under non-aqueous conditions, and utilize in the basic conditions
Potassium borohydride is reduced to it, and its synthesis preparation method is comprised the following steps that：
In the step (1) shown in step S100, according to catalyst synthetic ratio, palladium acetylacetonate is weighed or measured respectively
0.05g, silver acetate 0.15g, Graphene 35g, NMP0.1L, are impregnated in the reactor with stirring and heater, temperature
Degree is controlled to 100 DEG C, and normal pressure stirs 8h；
In the step (2) shown in step S200, by above-mentioned mixed liquor centrifugation, take solid matter and washed with absolute ethyl alcohol
Dried after washing suction filtration 2~3 times, maintained 4 hours at 220 DEG C；
In the step (3) shown in step S300, potassium hydroxide and potassium borohydride deionized water are configured to alkalescence molten
Liquid, pH value control is 30% in 9~12, wherein potassium borohydride mass concentration in the solution, and step (2) solid matter is added
In alkaline solution, maintain temperature 90 DEG C 8 hours, and continue stirring, after the completion of centrifugation take solid matter, completely cut off air containment
Preserve with standby.
Embodiment 2
A kind of graphene-based catalyst of high concentration preparation of ethylene through selective hydrogenation of acetylene, its active component is Pd and Ag, its load
Body is Graphene, and with N-methyl pyrrolidones (NMP) as solvent, is synthesized under non-aqueous conditions, and utilize in the basic conditions
Potassium borohydride is reduced to it, and its synthesis preparation method is comprised the following steps that：
In the step (1) shown in step S100, according to catalyst synthetic ratio, weigh respectively palladium acetylacetonate 0.01g,
Silver acetate 0.05g, Graphene 35g, NMP0.1L, are impregnated, temperature control in the reactor with stirring and heater
It it is 80 DEG C, normal pressure stirs 6h；
In the step (2) shown in step S200, by above-mentioned mixed liquor centrifugation, take solid matter and washed with absolute ethyl alcohol
Dried after washing suction filtration 2~3 times, maintained 6 hours at 200 DEG C.
In the step (3) shown in step S300, potassium hydroxide and potassium borohydride deionized water are configured to alkalescence molten
Liquid, 9~12, wherein mass concentration is 20% to potassium borohydride in the solution, and step (2) solid matter is added into alkali for pH value control
Property solution in, maintain temperature 70 C, 4 hours time, and continue stirring, after the completion of centrifugation take solid matter, completely cut off air
Closed preservation is with standby；
Embodiment 3
A kind of graphene-based catalyst of high concentration preparation of ethylene through selective hydrogenation of acetylene, its active component is Pd and Ag, its load
Body is Graphene, and with N-methyl pyrrolidones (NMP) as solvent, is synthesized under non-aqueous conditions, and utilize in the basic conditions
Potassium borohydride is reduced to it, and its synthesis preparation method is comprised the following steps that：
In the step (1) shown in step S100, according to catalyst synthetic ratio, weigh respectively palladium acetylacetonate 0.1g,
Silver acetate 0.5g, Graphene 35g, NMP0.1L, are impregnated, temperature control in the reactor with stirring and heater
It it is 120 DEG C, normal pressure stirs 12h；
In the step (2) shown in step S200, by above-mentioned mixed liquor centrifugation, take solid matter and washed with absolute ethyl alcohol
Dried after washing suction filtration 2~3 times, maintained 2 hours at 210 DEG C.
In the step (3) shown in step S300, potassium hydroxide and potassium borohydride deionized water are configured to alkalescence molten
Liquid, 9~12, wherein mass concentration is 40% to potassium borohydride in the solution, and step (2) solid matter is added into alkali for pH value control
Property solution in, maintain 80 DEG C of temperature, 6 hours time, and continue stirring, after the completion of centrifugation take solid matter, completely cut off air
Closed preservation is with standby；
Embodiment 4
A kind of application process of high concentration preparation of ethylene through selective hydrogenation of acetylene, it is by after wet method preparation purification with calcium carbide
High concentration acetylene is raw material, by the effect of catalyst, the method for synthesizing ethylene in the slurry bed system in containing nmp solvent.Its tool
Body step is as follows：
Graphene-based catalyst is added to the paste state bed reactor equipped with nmp solvent, nitrogen is passed first into by slurry
Bed reactor bottom bubbling, catches up with air in solution net and makes in paste state bed reactor under the conditions of nitrogen atmosphere, to introduce by electricity
The acetylene gas that stone generator is produced, is passed directly into paste state bed reactor after acetylene gas is purified, and acetylene volumetric concentration is more than
98.0%, while introducing hydrogen of the volumetric concentration more than 99.0%, hydrogen and acetylene are controlled with mol ratio as 4-8:1, operation is empty
Speed is 30000ml/ (g-cath), and during gas is passed through in slurry reactor by bottom, operating pressure is normal pressure, reaction temperature control
System is in 130 DEG C, successive reaction, after the gas-phase product as ethene of the paste state bed reactor top outflow being collected into after temperature rise stabilization
Product.
The present invention has passed through experimental verification of the selective catalysis Hydrogenation for ethene, the step of used during checking and specific implementation
Step is essentially identical shown in mode, and the detection of indices uses gas chromatographic analysis, wherein conversion of alkyne and life after experiment
Selective calculation into ethene is respectively：
In formula, C is the percentage composition of product gas, CcnIt is high polymer percentage composition.
Catalyst proportion and its application process gained the result see the table below
Table 1
| Checking example | 1 | 2 | 3 | 4 |
| Palladium acetylacetonate g | 0.02 | 0.05 | 0.08 | 0.1 |
| Silver acetate g | 0.05 | 0.15 | 0.32 | 0.5 |
| Graphene g | 35 | 35 | 35 | 35 |
| Hydrogen and acetylene molar ratio | 4:1 | 5:1 | 6:1 | 8:1 |
| Reaction temperature DEG C | 120 | 130 | 140 | 150 |
| Conversion of alkyne % | 96.5 | 100 | 100 | 100 |
| Ethylene selectivity % | 92.5 | 96.2 | 91.3 | 87.4 |
| Catalyst life h | 284 | 300 | 264 | 251 |
As can be seen that the graphene-based catalysis of application high concentration preparation of ethylene through selective hydrogenation of acetylene of the invention from proof list
Agent and its application process, every measurement index are preferable.Wherein, it is unstripped gas selective catalysis Hydrogenation to use high concentration acetylene gas
Standby ethene, by present invention checking example 2, up to 100%, the selectivity of ethene is also up to 96.2% to conversion of alkyne, and effect is bright
(wherein acetylene turns transformation efficiency in the aobvious preparation of ethylene through selective hydrogenation of acetylene better than disclosed in granted patent (CN101402541)
Rate is 100%, and ethylene selectivity is up to 86%).Meanwhile, catalyst life is more long.
Embodiment described above only expresses embodiments of the present invention, and its description is more specific and detailed, but can not
Therefore it is interpreted as the limitation to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art,
Without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to protection model of the invention
Enclose.Therefore, the protection domain of patent of the present invention should be determined by the appended claims.
Claims (10)
1. a kind of synthetic method of the graphene-based catalyst of high concentration preparation of ethylene through selective hydrogenation of acetylene, comprises the following steps：
Step (1)：Palladium acetylacetonate, silver acetate, Graphene, N-methyl pyrrolidones are carried out in reactor according to a certain ratio
Dipping composition mixed liquor；
Step (2)：The solid matter washing drying that the mixed liquor in step (1) is centrifugally separating to obtain；
Step (3)：Potassium hydroxide and potassium borohydride deionized water are configured to alkaline solution, will be described solid in step (2)
Body material is persistently stirred at a certain temperature in adding the alkaline solution, is then centrifugally separating to obtain graphene-based catalyst.
2. the synthetic method of graphene-based catalyst as claimed in claim 1, it is characterised in that acetyl described in step (1)
Acetone palladium, silver acetate, Graphene, the proportioning of N-methyl pyrrolidones are 0.01~0.1g:0.05~0.5g:35g:0.1L.
3. the synthetic method of graphene-based catalyst as claimed in claim 1, it is characterised in that impregnated described in step (1)
Carried out at 80~120 DEG C.
4. the synthetic method of graphene-based catalyst as claimed in claim 1, it is characterised in that dried described in step (2)
Carried out at 200~220 DEG C.
5. the synthetic method of graphene-based catalyst as claimed in claim 1, it is characterised in that certain described in step (3)
Temperature is 70~90 DEG C.
6. a kind of application process of graphene-based catalyst as any one of claim 1-5, comprises the following steps：
Step 1)：The graphene-based catalyst is added to the paste state bed reactor equipped with N-methyl pyrrolidinone solvent,
Nitrogen bubble is passed through by the paste state bed reactor bottom；
Step 2)：Under the conditions of the paste state bed reactor is nitrogen atmosphere, the acetylene gas produced by carbide generator, institute are introduced
State acetylene gas it is purified after be passed directly into the paste state bed reactor, while introducing hydrogen, gas is passed through the slurry by bottom
In state bed reactor under uniform temperature and pressure successive reaction；
Step 3)：The gas-phase product of paste state bed reactor top outflow is collected, that is, obtains ethylene product.
7. the application process of graphene-based catalyst as claimed in claim 6, it is characterised in that the step 2) in, it is described
Hydrogen and the acetylene molar ratio are 4~8:1.
8. the application process of graphene-based catalyst as claimed in claims 6 or 7, it is characterised in that acetylene volumetric concentration is big
In 98.0%.
9. the application process of graphene-based catalyst as claimed in claims 6 or 7, it is characterised in that the hydrogen volume is dense
Degree is more than 99.0%.
10. the graphene-based catalyst that a kind of method as any one of claim 1-5 is prepared.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2171719A (en) * | 1985-02-26 | 1986-09-03 | South African Inventions | Hydrogenation of unsaturated aliphatic hydrocarbons |
| CN101745389A (en) * | 2009-12-29 | 2010-06-23 | 大连理工大学 | A kind of egg-shell catalyst that is used for preparation of ethylene through selective hydrogenation of acetylene |
| CN102489225A (en) * | 2011-12-10 | 2012-06-13 | 太原理工大学 | Slurry bubble column technology for preparing ethylene through acetylene hydrogenation and device thereof |
| CN103044179A (en) * | 2012-12-19 | 2013-04-17 | 清华大学 | Method for preparing ethylene through liquid-phase selective hydrogenation of acetylene in slurry reactor |
| CN204522947U (en) * | 2015-05-15 | 2015-08-05 | 北京神雾环境能源科技集团股份有限公司 | For paste state bed reactor and the reaction system of preparing ethylene by selective hydrogenation of acetylene |
| CN105879863A (en) * | 2014-12-10 | 2016-08-24 | 苏党生 | Novel carrier loading palladium catalyst applied to acetylene selective hydrogenation |
-
2017
- 2017-02-27 CN CN201710109283.7A patent/CN106902820A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2171719A (en) * | 1985-02-26 | 1986-09-03 | South African Inventions | Hydrogenation of unsaturated aliphatic hydrocarbons |
| CN101745389A (en) * | 2009-12-29 | 2010-06-23 | 大连理工大学 | A kind of egg-shell catalyst that is used for preparation of ethylene through selective hydrogenation of acetylene |
| CN102489225A (en) * | 2011-12-10 | 2012-06-13 | 太原理工大学 | Slurry bubble column technology for preparing ethylene through acetylene hydrogenation and device thereof |
| CN103044179A (en) * | 2012-12-19 | 2013-04-17 | 清华大学 | Method for preparing ethylene through liquid-phase selective hydrogenation of acetylene in slurry reactor |
| CN105879863A (en) * | 2014-12-10 | 2016-08-24 | 苏党生 | Novel carrier loading palladium catalyst applied to acetylene selective hydrogenation |
| CN204522947U (en) * | 2015-05-15 | 2015-08-05 | 北京神雾环境能源科技集团股份有限公司 | For paste state bed reactor and the reaction system of preparing ethylene by selective hydrogenation of acetylene |
Non-Patent Citations (1)
| Title |
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| 胡佳玮: "纳米Pd负载型催化剂的可控制备及其在苯乙炔选择性加氢中的应用", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
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