CN106345490A - Dual-ingredient alkyne hydrogenation reaction catalyst - Google Patents
Dual-ingredient alkyne hydrogenation reaction catalyst Download PDFInfo
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- CN106345490A CN106345490A CN201610709258.8A CN201610709258A CN106345490A CN 106345490 A CN106345490 A CN 106345490A CN 201610709258 A CN201610709258 A CN 201610709258A CN 106345490 A CN106345490 A CN 106345490A
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- Prior art keywords
- catalyst
- ingredient
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- weight
- carrier
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- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 19
- 150000001345 alkine derivatives Chemical class 0.000 title claims abstract description 17
- 239000004615 ingredient Substances 0.000 title abstract 8
- 239000007809 chemical reaction catalyst Substances 0.000 title abstract 4
- 239000003054 catalyst Substances 0.000 claims abstract description 39
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000000919 ceramic Substances 0.000 claims abstract description 12
- 239000000843 powder Substances 0.000 claims abstract description 10
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims abstract description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052802 copper Inorganic materials 0.000 claims abstract description 7
- 239000010949 copper Substances 0.000 claims abstract description 7
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 6
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 239000005457 ice water Substances 0.000 claims description 3
- 238000005470 impregnation Methods 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 235000011164 potassium chloride Nutrition 0.000 claims description 3
- 239000001103 potassium chloride Substances 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- 229910000077 silane Inorganic materials 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 2
- 229910000423 chromium oxide Inorganic materials 0.000 claims description 2
- 238000003672 processing method Methods 0.000 claims description 2
- 150000001336 alkenes Chemical class 0.000 abstract description 6
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 4
- 238000006384 oligomerization reaction Methods 0.000 abstract description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 abstract description 2
- 239000011651 chromium Substances 0.000 abstract description 2
- 238000002156 mixing Methods 0.000 abstract description 2
- 239000004480 active ingredient Substances 0.000 abstract 1
- 150000001337 aliphatic alkines Chemical class 0.000 abstract 1
- 230000003197 catalytic effect Effects 0.000 abstract 1
- 229910052804 chromium Inorganic materials 0.000 abstract 1
- 230000002035 prolonged effect Effects 0.000 abstract 1
- 150000001993 dienes Chemical class 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- ZWPVWTIRZYDPKW-UHFFFAOYSA-N chromium(VI) oxide peroxide Inorganic materials [O-2].[O-][Cr]([O-])(=O)=O ZWPVWTIRZYDPKW-UHFFFAOYSA-N 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- -1 ethylene, propylene, butylene Chemical group 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
Classifications
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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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8926—Copper and noble metals
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
-
- B01J35/19—
-
- 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
- C07C5/08—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of carbon-to-carbon triple bonds
- C07C5/09—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of carbon-to-carbon triple bonds to carbon-to-carbon double bonds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/148—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound
- C07C7/163—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound by hydrogenation
- C07C7/167—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound by hydrogenation for removal of compounds containing a triple carbon-to-carbon bond
Abstract
The invention discloses a dual-ingredient alkyne hydrogenation reaction catalyst, and relates to the technical field of a catalyst. The dual-ingredient alkyne hydrogenation reaction catalyst consists of an ingredient A catalyst and an ingredient B catalyst according to a weight ratio of 3:1, wherein for the ingredient A catalyst, ceramic micro powder is used as a carrier, and copper is used as an auxiliary active ingredient, wherein palladium accounts for 10 to 15 percent of the total weight of the carrier, and the copper accounts for 3 to 5 percent of the total weight of the carrier; the ingredient B catalyst is formed by mixing chromium hemitrioxide and phosphorus pentoxide according to the weight ratio of 2:1. The alkyne hydrogenation reaction catalyst is prepared in a dual-ingredient mode; the catalyst has high hydrogenation selectivity on alkine and dialkene; the monoolefine loss quantity is greatly reduced; the catalytic activity is high; the hydrogenation reaction temperature can be lowered to 50 DEG C or above, so that the pollution on the catalyst by olefin oligomerization is reduced; the service life of the catalyst is prolonged.
Description
Technical field:
The present invention relates to catalyst technical field is and in particular to a kind of double-component alkynes catalyst for hydrogenation.
Background technology:
During hydrocarbon cracking alkene, generating ethylene, propylene, butylene and butadiene produce part alkynes simultaneously and
Alkadienes.It is objectionable impurities that these alkynes and alkadienes are processed particularly in olefin polymerization process after alkene, needs to remove.Choosing
Selecting hydrogenation and being allowed to become corresponding monoolefine is most economical and the most received method.Wherein, selective hydrogenation catalyst
Using very crucial, need catalyst to have good selectivity, only monoolefine is not lost to alkynes and diene hydrogenation；And
And catalyst will have good activity, reacts at a lower temperature, reduce and by olefin(e) oligomerization, catalyst is polluted, and
Catalyst is led to inactivate.
Content of the invention:
The technical problem to be solved is to provide that a kind of selectivity is strong, activity is high and double groups of long service life
Part alkynes catalyst for hydrogenation.
The technical problem to be solved to be realized using following technical scheme:
A kind of double-component alkynes catalyst for hydrogenation, by the first component catalyst than 3:1 for the weight and component B catalyst
Composition, described first component catalyst using ceramic as carrier, active component based on palladium, copper be help active component, wherein
Palladium accounts for the 10-15% of total weight of carrier, and copper accounts for the 3-5% of total weight of carrier；Described component B catalyst oxygen than 2:1 by weight
Change chromium and phosphorus pentoxide mixes.
The preparation method of described first component catalyst is: Palladous chloride., copper chloride and potassium chloride are mixed by weight 2:1:0.5
Add water after conjunction and be made into the impregnation liquid of mass concentration 20-30%, and add the ceramic of 3-5 times of Palladous chloride. weight, fully dispersed
Afterwards stand 30min, microwave treatment 5min under microwave frequency 2450mhz, power 700w, process terminate after under ice-water bath with
The speed of 10 DEG C/min is lowered the temperature, and continues after temperature is down to 35-45 DEG C under microwave frequency 2450mhz, power 700w
Microwave treatment 3min, then naturally cools to room temperature, and gained mixture is sent in freezer dryer, becomes through abundant crushed after being dried
Powder, finally by gained powder at 450-500 DEG C roasting 3h.
Using front through pretreatment, its processing method is described ceramic: first adds equivalent to mix 20 parts of ceramics
Close in solution, by weight, the Oleum Terebinthinae than 1:1 is mixed, fully this mixed solution with the dilute nitric acid solution of mass concentration 40%
Moistening stands 3h at 0-5 DEG C, and supersound process 15min under supersonic frequency 40khz, power 100w, is subsequently adding 1.5 parts
Spermol and 1 part of silane coupler, mix homogeneously microwave treatment 5min, mistake under microwave frequency 2450mhz, power 700w
Filter, gained filtering residue is dried 8h prior to 100-110 DEG C, then at 500-550 DEG C of roasting 2h, last grind into powder.
The invention has the beneficial effects as follows: the present invention adopts double-component form that alkynes catalyst for hydrogenation, this catalysis are obtained
Agent is high to the hydrogenation selectivity of alkynes and alkadienes, substantially reduces the loss amount of monoolefine；And catalysis activity is strong, can will be hydrogenated with
Reaction temperature reduces by more than 50 DEG C, thus reducing pollution catalyst being caused by olefin(e) oligomerization, extends the use longevity of catalyst
Life.
Specific embodiment:
In order that technological means, creation characteristic, reached purpose and effect that the present invention realizes are easy to understand, tie below
Close specific embodiment, the present invention is expanded on further.
The preparation of first component catalyst: 2g Palladous chloride., 1g copper chloride and 0.5g potassium chloride are added water and is made into mass concentration
30% impregnation liquid, and add 6g ceramic, fully dispersed rear standing 30min, then at microwave frequency 2450mhz, power
Microwave treatment 5min under 700w, process is lowered the temperature with the speed of 10 DEG C/min after terminating under ice-water bath, treats that temperature is down to 35-
Continue microwave treatment 3min under microwave frequency 2450mhz, power 700w after 45 DEG C, then naturally cool to room temperature, gained
Mixture is sent in freezer dryer, becomes powder through abundant crushed after being dried, finally by the roasting at 450-500 DEG C of gained powder
3h.
After testing, palladium accounts for the 12.67% of total weight of carrier, and copper accounts for the 3.95% of total weight of carrier.
Component B catalyst is mixed by the chromium oxide than 2:1 for the weight and phosphorus pentoxide.
First component catalyst is sufficiently mixed than 3:1 with weight with component B catalyst, that is, double-component alkynes hydrogenation is obtained
Catalysts.
The pretreatment of ceramic: first add 20g ceramic in mixed in equal amounts solution, this mixed solution is by weight ratio
The Oleum Terebinthinae of 1:1 is mixed with the dilute nitric acid solution of mass concentration 40%, and abundant moistening stands 3h at 0-5 DEG C, and in
Supersound process 15min under supersonic frequency 40khz, power 100w, is subsequently adding 1.5g spermol and 1g silane coupler, and mixing is all
Even microwave treatment 5min under microwave frequency 2450mhz, power 700w, filters, gained filtering residue is prior to 100-110 DEG C of drying
8h, then at 500-550 DEG C of roasting 2h, last grind into powder.
Ultimate principle and principal character and the advantages of the present invention of the present invention have been shown and described above.The technology of the industry
, it should be appreciated that the present invention is not restricted to the described embodiments, the simply explanation described in above-described embodiment and description is originally for personnel
The principle of invention, without departing from the spirit and scope of the present invention, the present invention also has various changes and modifications, these changes
Change and improvement both falls within scope of the claimed invention.Claimed scope by appending claims and its
Equivalent thereof.
Claims (3)
1. a kind of double-component alkynes catalyst for hydrogenation it is characterised in that: by the first component catalyst than 3:1 for the weight and second group
Part catalyst composition, described first component catalyst using ceramic as carrier, active component based on palladium, copper is to help activearm
Point, wherein palladium accounts for the 10-15% of total weight of carrier, and copper accounts for the 3-5% of total weight of carrier；Described component B catalyst is by weight ratio
The chromium oxide of 2:1 and phosphorus pentoxide mix.
2. double-component alkynes catalyst for hydrogenation according to claim 1 is it is characterised in that described first component catalyst
Preparation method be: add water after Palladous chloride., copper chloride and potassium chloride are mixed by weight 2:1:0.5 and be made into mass concentration 20-
30% impregnation liquid, and add the ceramic of 3-5 times of Palladous chloride. weight, fully dispersed rear standing 30min, then at microwave frequency
Microwave treatment 5min under 2450mhz, power 700w, process is lowered the temperature with the speed of 10 DEG C/min after terminating under ice-water bath,
Continue microwave treatment 3min under microwave frequency 2450mhz, power 700w after temperature is down to 35-45 DEG C, then naturally cold
But to room temperature, gained mixture send into freezer dryer in, become powder through abundant crushed after being dried, finally by gained powder in
Roasting 3h at 450-500 DEG C.
3. double-component alkynes catalyst for hydrogenation according to claim 1 it is characterised in that: described ceramic uses
Front through pretreatment, its processing method is: first adds 20 parts of ceramics in mixed in equal amounts solution, this mixed solution is by weight
Oleum Terebinthinae than 1:1 is mixed with the dilute nitric acid solution of mass concentration 40%, and abundant moistening stands 3h at 0-5 DEG C, and
Supersound process 15min under supersonic frequency 40khz, power 100w, is subsequently adding 1.5 parts of spermols and 1 part of silane coupler, mixes
Close uniformly microwave treatment 5min under microwave frequency 2450mhz, power 700w, filter, gained filtering residue is dry prior to 100-110 DEG C
Dry 8h, then at 500-550 DEG C of roasting 2h, last grind into powder.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610709258.8A CN106345490A (en) | 2016-08-23 | 2016-08-23 | Dual-ingredient alkyne hydrogenation reaction catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610709258.8A CN106345490A (en) | 2016-08-23 | 2016-08-23 | Dual-ingredient alkyne hydrogenation reaction catalyst |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106345490A true CN106345490A (en) | 2017-01-25 |
Family
ID=57844636
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610709258.8A Pending CN106345490A (en) | 2016-08-23 | 2016-08-23 | Dual-ingredient alkyne hydrogenation reaction catalyst |
Country Status (1)
| Country | Link |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101081366A (en) * | 2007-02-02 | 2007-12-05 | 中国石油天然气股份有限公司长庆石化分公司 | Pd radicel duplex metal selective hydrogenation catalyzer and method for preparing the same and application thereof |
| CN102125839A (en) * | 2011-01-21 | 2011-07-20 | 北京三聚环保新材料股份有限公司 | Alkyne hydrogenation catalyst and preparation method thereof |
| CN102614870A (en) * | 2012-03-20 | 2012-08-01 | 中国平煤神马能源化工集团有限责任公司 | Vinylacetylene hydrogenation catalyst and preparation method thereof |
| CN104437467A (en) * | 2014-10-27 | 2015-03-25 | 杭州聚力氢能科技有限公司 | Hydrogenation catalyst, application of hydrogenation catalyst, dehydrogenation catalyst and application of dehydrogenation catalyst |
-
2016
- 2016-08-23 CN CN201610709258.8A patent/CN106345490A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101081366A (en) * | 2007-02-02 | 2007-12-05 | 中国石油天然气股份有限公司长庆石化分公司 | Pd radicel duplex metal selective hydrogenation catalyzer and method for preparing the same and application thereof |
| CN102125839A (en) * | 2011-01-21 | 2011-07-20 | 北京三聚环保新材料股份有限公司 | Alkyne hydrogenation catalyst and preparation method thereof |
| CN102614870A (en) * | 2012-03-20 | 2012-08-01 | 中国平煤神马能源化工集团有限责任公司 | Vinylacetylene hydrogenation catalyst and preparation method thereof |
| CN104437467A (en) * | 2014-10-27 | 2015-03-25 | 杭州聚力氢能科技有限公司 | Hydrogenation catalyst, application of hydrogenation catalyst, dehydrogenation catalyst and application of dehydrogenation catalyst |
Non-Patent Citations (1)
| Title |
|---|
| 李远志等: "双烯或炔烃选择性加氢的研究", 《三峡大学学报（自然科学版）》 * |
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Application publication date: 20170125 |
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