CN1051478C - Catalyst for etherification of olefine and preparing process thereof - Google Patents
Catalyst for etherification of olefine and preparing process thereof Download PDFInfo
- Publication number
- CN1051478C CN1051478C CN96109509A CN96109509A CN1051478C CN 1051478 C CN1051478 C CN 1051478C CN 96109509 A CN96109509 A CN 96109509A CN 96109509 A CN96109509 A CN 96109509A CN 1051478 C CN1051478 C CN 1051478C
- Authority
- CN
- China
- Prior art keywords
- catalyst
- carrier
- solution
- active metal
- metal component
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Abstract
The present invention relates to a catalyst for alkene etherification and a preparing process thereof. The catalyst is composed of active metal components, a cocatalyst and a carrier, wherein the cocatalyst is chosen from the soluble salts of elements in the third and/or the fourth main groups in the periodic table, so the catalyst has the advantages of high stability, long service life, high activity in selective hydrogenation and double-bond isomerization, etc. when used in etherification reaction and/or selective hydrogenation reaction of C3-C7 alkene.
Description
The present invention relates to a kind of C
3～C
7Etherification of olefins reaction and/or selective hydrogenation catalyst and method for making thereof.
Tert amyl methyl ether(TAME) (TAME) and senior ether thereof are the good additives that improves octane number, and are the important composition compositions of reformulated gasoline, and its main route of synthesis is the C that adopts in catalytic cracking and the drippolene
5Fraction and light petrol fraction thereof and methyl alcohol carry out etherification reaction, and catalyst system therefor is a Hydrogen macropore strong acid cation exchanger resin.Yet the C in catalytic cracking and drippolene
5Exist the conjugated diene of 0.4～2.0wt% in fraction and the light petrol fraction thereof, the poly reaction can take place in these conjugated dienes under the effect of Hydrogen macropore strong acid cation exchange resin catalyst, generate dimer, trimer and high polymer.These polymer not only exist in the product, and product quality is descended, and can deposit on the surface attached to catalyst, and duct that can blocking catalyst, cause catalyst to shorten service life and non-renewable, have reduced the economic benefit of device.
One of ways of addressing this issue is to adopt the resin catalyst that is loaded with metal, under the hydro condition, also exists the selective hydrogenation of diolefin and the double bond isomerization reaction of part alkene when carrying out the reaction of alkene and methanol etherification.This metallic Hydrogen macropore strong acid cation exchange resin catalyst is to adopt ion-exchange and infusion process directly to be stated from the reactive metal element on the carrier as US4330679, US5141525, US4950820, EP490571 are disclosed, reactive metal unit have transition metal such as Pt, Pd, Cr, Rh, Fe, Ni, they can be metallic states or be sulfide that carrier is storng-acid cation exchange resin and Al
2O
3But this catalyst still has reactive metal element load instability, the defective that life of catalyst is short.
The objective of the invention is to overcome the reactive metal element load instability that above-mentioned containing metal acid cation exchange resin catalyst exists, the defective that life of catalyst is short, a kind of etherification of olefine catalysts is proposed, it is made up of active metal component, co-catalyst and carrier, and this catalyst has long and selective hydrogenation and the active advantages of higher of double-bond isomerization of stable high life.
To describe catalyst of the present invention and method for making thereof and purposes in detail below.
Etherification of olefine catalysts of the present invention is characterized in that being made up of active metal component, co-catalyst and carrier, wherein:
Active metal component is one or more in Pt, Ni, Pd, Co, Cu metal or its corresponding soluble-salt, and the content of active metal component is counted 0.05～9wt% with the weight of metallic element in the catalyst, is preferably 0.1～0.4wt%;
Carrier is an acid cation exchange resin;
Co-catalyst is one or more in the soluble salt of the 3rd major element and the 4th major element in the periodic table of elements, it is to be carried on the above-mentioned carrier by infusion process or ion-exchange, the content of modifier is counted 0.05～10g with the weight of major element in every liter of carrier, is preferably 0.15～5g.
Above-mentioned active metal component is better with the soluble-salt of choosing metal Pt, Ni, Pd, Co, Cu, generally adopts chlorate, bromate, iodate, sulfate, nitrate or acetate a kind of of these metals or their mixture.
Above-mentioned co-catalyst is better with the soluble-salt of choosing Si, Al, Ge, B, Sn or Ga element, generally adopts chlorate, bromate, iodate, sulfate, nitrate or acetate a kind of of these metals or their mixture.
Preparation of catalysts method of the present invention, can carry out as follows:
(1) carrier is dipped in the solution of co-catalyst, soak 0.2～12 hour under the room temperature after, be washed with water to filtrate and show neutral, obtain the carrier of modification more after drying;
(2) carrier with modification is dipped in the solution of active metal component, soak 0.2～24 hour under the room temperature after, be washed with water to filtrate and show neutral, again through air dry or in reductant solution 50～120 ℃ of constant temperature reduction obtain catalyst after 0.5～10 hour.
The Preparation of catalysts method also can be carried out as follows:
Carrier is dipped in the solution of active metal component, soak 0.2～24 hour under the room temperature after, be washed with water to filtrate and show neutral, dry or 50～120 ℃ of constant temperature reduction after 0.5～10 hour in reductant solution through air again; Again it is dipped in the solution of co-catalyst, soak 0.2～12 hour under the room temperature after, drying obtains catalyst again.
Employed reducing agent can be formic acid, hydrogen, urea etc. in the said method.
Catalyst of the present invention can be used in C3～C7 etherification of olefins reaction and/or the selective hydrogenation, especially for the C that contains isomeric olefine
5In the etherification reaction of fraction and light petrol fraction thereof and alcohol and/or the isomerization reaction of selective hydrogenation and/or olefinic double bonds.
The maximum characteristics of catalyst of the present invention are by the processing of co-catalyst to the resin cation carrier; make it to have more stable surface; play protection simultaneously, isolate the reactive metal effect; guarantee that reactive metal stably is present in the resin catalyst surface, improved the service life of catalyst.Simultaneously, owing to the effect of co-catalyst, improved the activity of selection of catalysts hydrogenation and double bond isomerization reaction.
Further set forth Catalysts and its preparation method of the present invention with example below.
Example 1 takes by weighing palladium nitrate Pd (NO
3)
22H
2The O150.3 milligram is dissolved in the distilled water, is made into 100 ml solns.(S that extraordinary resin processing plant produces is gone in in a big way in Beijing with 58 milliliters Hydrogen macropore strong acid cation exchanger resins
54) immerse in the above-mentioned solution, ion-exchange was used the distilled water filtering and washing after 2 hours, was washed till filtrate and showed till the neutrality.Place air drying to use after a couple of days.Promptly get the catalyst A that the Pd tenor is 0.26wt%.
Example 2 is measured 0.1N Al (NO
3)
3Solution 2.22ml, and be made into 100 ml solns with distilled water, (S that extraordinary resin processing plant produces is gone in in a big way in Beijing with 58 milliliters Hydrogen macropore strong acid cation exchanger resins
54) immerse in the above-mentioned solution, ion-exchange was used the distilled water filtering and washing after 4 hours, was washed till filtrate and showed till the neutrality.Taking-up places 90～100 ℃ of following thermostatted waters to vacuumize dry 3 hours.Promptly get the resin carrier of the co-catalyst that contains 0.15 gram in every liter dry resin.This carrier is pressed Pd metallic element in the example 1 step load, and its content is 0.26wt%.Then with 100 milliliters of the formic acid solutions of 7N, in 80 ℃ of following constant temperature reductase 12s hour.Till showing neutrality with distilled water washing then, obtain catalyst B after placing air drying.
Example 3 is measured 0.1N Al (NO
3)
3Solution 4.44ml, and be made into 100 ml solns with distilled water, (S that extraordinary resin processing plant produces is gone in in a big way in Beijing with 58 milliliters Hydrogen macropore strong acid cation exchanger resins
54) immerse in the above-mentioned solution, ion-exchange was used the distilled water filtering and washing after 4 hours, was washed till filtrate and showed till the neutrality.Taking-up places 90～100 ℃ of following thermostatted waters to vacuumize dry 3 hours.Promptly get the resin carrier of the co-catalyst that contains 0.30 gram in every liter dry resin.This carrier is pressed Pd metallic element in the example 1 step load, and its content is 0.26wt%, obtains catalyst C after the drying.
Example 4: measure 0.1N H
3BO
3Solution 4.44ml, and be made into 50 ml solns with distilled water, (S that extraordinary resin processing plant produces is gone in in a big way in Beijing with 58 milliliters Hydrogen macropore strong acid cation exchanger resins
54) immerse in the above-mentioned solution, ion-exchange was used the distilled water filtering and washing after 4 hours, was washed till filtrate and showed till the neutrality.Taking-up places 90～100 ℃ of following thermostatted waters to vacuumize dry 3 hours.Promptly get the resin carrier of the co-catalyst that contains 1.5 grams in every liter dry resin.This carrier is pressed Pd metallic element in the example 1 step load, and its content is 0.26wt%, obtains catalyst D after the drying.
Example 5 experimental conditions are used 0.1N SnCl with example 4
4Solution replaces 0.1N H for 0.51 milliliter
3BO
3Solution obtains catalyst E.
Example 6 is estimated the active and stable of above-mentioned catalyst A, B, C, D, E in a small-sized continuous pressurization static bed reaction unit.Reaction condition is: 13 milliliters of catalyst amounts, and 70 ℃ of reaction temperatures, liquid amasss air speed 6.0h
-1, hydrogen flowing quantity is 6.0～8.0ml/min.The content of Main Ingredients and Appearance is in the reactant liquor: 3-methyl-1-butene 1.97wt%, 2-methyl-1-butene alkene 12.21wt%, 2-methyl-2-2 butylene 14.50wt%, diolefin 0.455wt%, methyl alcohol 10.90wt%.Evaluation result sees Table 1.
| Catalyst type | Catalyst A | Catalyst B | Catalyst C | Catalyst D | Catalyst E | |||||
| Reaction time hr | 4 | 5 | 4 | 6 | 4 | 11 | 4 | 8 | 4 | 9 |
| 3-methyl isophthalic acid-butylene (wt%) | 1.47 | 1.58 | 1.17 | 1.58 | 0.22 | 0.79 | 0.906 | 1.708 | 0.881 | 1.094 |
| 2-methyl-1-butene alkene (wt%) | 1.54 | 1.84 | 1.02 | 0.89 | 1.18 | 1.04 | 1.78 | 1.24 | 1.83 | 1.01 |
| 2-methyl-2-butene (wt%) | 9.83 | 9.77 | 9.49 | 8.74 | 10.76 | 9.81 | 10.34 | 9.84 | 10.55 | 9.80 |
| Diolefin (ppm) | 360 | 975 | 110 | 360 | 150 | 100 | 50 | 170 | 0 | 100 |
| TAME(wt％) | 18.24 | 17.90 | 20.55 | 20.89 | 19.65 | 20.49 | 19.45 | 20.40 | 20.11 | 20.87 |
| TAME yield % | 52.4 | 51.4 | 57.3 | 59.9 | 53.0 | 56.5 | 52.4 | 55.7 | 52.7 | 57.0 |
| Double-bond isomerism conversion ratio (%) | 25.4 | 19.8 | 40.6 | 19.8 | 88.8 | 59.9 | 54.0 | 45.3 | 55.3 | 44.5 |
Claims (9)
1, a kind of etherification of olefine catalysts is characterized in that being made up of active metal component, co-catalyst and carrier, wherein:
Active metal component is one or more in Pt, Ni, Pd, Co, Cu metal or its corresponding soluble-salt, and the content of active metal component is counted 0.05wt～9wt% with the weight of metallic element in the catalyst;
Carrier is an acid cation exchange resin;
Co-catalyst is one or more in the soluble salt of the 3rd major element and the 4th major element in the periodic table of elements, it is to be carried on the above-mentioned carrier by infusion process or ion-exchange, and the content of modifier is counted 0.05～10g with the weight of major element in every liter of carrier.
2, catalyst according to claim 1 is characterized in that, described active metal component is chlorate, bromate, iodate, sulfate, nitrate or acetate a kind of of metal Pt, Ni, Pd, Co, Cu or their mixture.
3, catalyst according to claim 1 is characterized in that, described co-catalyst is soluble-salt a kind of of Si, Al, Ge, B, Sn or Ga or their mixture.
4, catalyst according to claim 1 is characterized in that, the content of described reactive metal element in catalyst is 0.1～0.4wt%.
5, catalyst according to claim 1 is characterized in that, the content of co-catalyst is counted 0.15～5g with the weight of major element in every liter of carrier.
6, the described Preparation of catalysts method of claim 1 comprises the steps:
(1) carrier is dipped in the solution of co-catalyst, soak 0.2～12 hour under the room temperature after, be washed with water to filtrate and show neutral, obtain the carrier of modification more after drying;
(2) carrier with modification is dipped in the solution of active metal component, soak 0.2～24 hour under the room temperature after, be washed with water to filtrate and show neutral, again through air dry or in reductant solution 50～120 ℃ of constant temperature reduction obtain catalyst after 0.5～10 hour;
Wherein said reducing agent is selected from a kind of in formic acid, hydrogen, the urea.
7, the described Preparation of catalysts method of claim 1 comprises the steps:
Carrier is dipped in the solution of active metal component, soak 0.2～24 hour under the room temperature after, be washed with water to filtrate and show neutral, dry or 50～120 ℃ of constant temperature reduction after 0.5～10 hour in reductant solution through air again; Again it is dipped in the solution of co-catalyst, soak 0.2～12 hour under the room temperature after, drying obtains catalyst;
Wherein said reducing agent is selected from a kind of in formic acid, hydrogen, the urea.
8, the purposes of the described catalyst of one of claim 1～5 is characterized in that, can be used in C3～C7 etherification of olefins reaction and/or the selective hydrogenation.
9, purposes according to claim 8 is characterized in that, is used to contain the C of isomeric olefine
5In the etherification reaction and/or selective hydrogenation of fraction and alcohol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96109509A CN1051478C (en) | 1996-08-21 | 1996-08-21 | Catalyst for etherification of olefine and preparing process thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96109509A CN1051478C (en) | 1996-08-21 | 1996-08-21 | Catalyst for etherification of olefine and preparing process thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1146927A CN1146927A (en) | 1997-04-09 |
| CN1051478C true CN1051478C (en) | 2000-04-19 |
Family
ID=5120392
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN96109509A Expired - Fee Related CN1051478C (en) | 1996-08-21 | 1996-08-21 | Catalyst for etherification of olefine and preparing process thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1051478C (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102557887B (en) * | 2010-12-17 | 2014-01-15 | 中国石油天然气股份有限公司 | Method for preparing tert-amyl methyl ether by etherifying C5 raffinate |
| CN111939926B (en) * | 2020-07-31 | 2023-03-24 | 扬州大学 | Cu-Zr oxide nanoparticle loaded Pd (II) catalyst and preparation method and application thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0210514A2 (en) * | 1985-07-24 | 1987-02-04 | Ec Erdölchemie Gmbh | Hydrogenation of olefinic hydrocarbons in t-alkyl-alkyl-ether-containing hydrocarbon fractions |
| DE3813689A1 (en) * | 1987-04-23 | 1988-11-17 | Bp Benzin Und Petroleum Ag | Process for the reaction of branched olefins with alkanols |
| CN1034705A (en) * | 1987-12-30 | 1989-08-16 | 无比石油公司 | Produce the method for ether |
| JPH04224539A (en) * | 1990-04-16 | 1992-08-13 | Texaco Chem Co | Process for producing tert-amyl methyl ether from c5 olefin fraction |
| CN1026331C (en) * | 1989-04-22 | 1994-10-26 | 抚顺石油学院 | Etherealization technique for olefine-hydrocarbon-bearing gasoline |
| CN1026332C (en) * | 1989-07-11 | 1994-10-26 | 抚顺石油学院 | Process for hydroetherification of olefin-containing gasoline |
| JPH0965712A (en) * | 1995-09-01 | 1997-03-11 | Iseki & Co Ltd | Root remover of bulbs of flowering plant |
-
1996
- 1996-08-21 CN CN96109509A patent/CN1051478C/en not_active Expired - Fee Related
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0210514A2 (en) * | 1985-07-24 | 1987-02-04 | Ec Erdölchemie Gmbh | Hydrogenation of olefinic hydrocarbons in t-alkyl-alkyl-ether-containing hydrocarbon fractions |
| DE3813689A1 (en) * | 1987-04-23 | 1988-11-17 | Bp Benzin Und Petroleum Ag | Process for the reaction of branched olefins with alkanols |
| CN1034705A (en) * | 1987-12-30 | 1989-08-16 | 无比石油公司 | Produce the method for ether |
| CN1026331C (en) * | 1989-04-22 | 1994-10-26 | 抚顺石油学院 | Etherealization technique for olefine-hydrocarbon-bearing gasoline |
| CN1026332C (en) * | 1989-07-11 | 1994-10-26 | 抚顺石油学院 | Process for hydroetherification of olefin-containing gasoline |
| JPH04224539A (en) * | 1990-04-16 | 1992-08-13 | Texaco Chem Co | Process for producing tert-amyl methyl ether from c5 olefin fraction |
| JPH0965712A (en) * | 1995-09-01 | 1997-03-11 | Iseki & Co Ltd | Root remover of bulbs of flowering plant |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1146927A (en) | 1997-04-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101239892B (en) | Method for preparing iso-butyraldehyde and isobutyl alcohol by methylacrolein hydrogenation | |
| DE3914817C2 (en) | Process for oligomerizing olefins | |
| Halpern et al. | Homogeneous Catalysis of the Hydrogenation of Olefinic Compounds by Ruthenium (II) Chloride1 | |
| CN100448527C (en) | Catalyst in preparation of isobutene by methyl tertbutyl ether pyrolysis | |
| WO2003035582A1 (en) | Hydrogenolysis of 6-carbon sugars and other organic compounds | |
| US3703461A (en) | Hydrogenation process and catalyst | |
| US4612301A (en) | Metal coordination complexes of heteropolyacids as catalysts for alcohol conversion | |
| CN101121899B (en) | Selectivity hydrogenation method for whole fraction crack petroleum | |
| CN1051478C (en) | Catalyst for etherification of olefine and preparing process thereof | |
| Didillon et al. | Surface Organometallic Chemistry on Metals; Selective hydrogenation of citral on silica supported Rhodium modified by tetra-n-butyl Germanium, Tin and Lead | |
| CN1032139C (en) | Polymer preparation | |
| US4687875A (en) | Metal coordination complexes of heteropolyacids as catalysts for alcohol conversion | |
| CN1145898A (en) | Process for producing aliphatic nitrile | |
| EP3978539A1 (en) | Method for preparing hydrogenated petroleum resin | |
| CN111229247A (en) | Catalyst for preparing ethanol by hydrogenation of oxalate and preparation method and application thereof | |
| CN107970929A (en) | A kind of alkynes and alkadienes liquid phase selective hydrogenation catalyst, preparation method and application | |
| CN1101261C (en) | Selective hydrogenation catalyst for alkyne and diene | |
| CN1380282A (en) | Catalyst for hydrogenation of dimethyl terephthalate to produce 1,4-dimethyl hexahydrophthalate and its preparation method | |
| Didillon et al. | Surface Organometallic Chemistry on Metals: Selective Hydrogenation of Citral into Geraniol and Nerol on Tin Modified Silica Supported Rhodium. | |
| CN1291783C (en) | Catalyst for producing dimethyl 1,4-cyclohexanedicarboxylate | |
| CN1039592C (en) | Process for producing hydrogenating catalyst | |
| US6049012A (en) | Catalyst and process for the production of alkyl tert alkyl ether from hydrocarbon feedstocks with high levels of sulfur | |
| CN1188493C (en) | Hydrocracking technology for increase production of low solidifying point diesel oil and ethylene producing raw material | |
| US5639927A (en) | Process of producing cycloolefin | |
| Hara et al. | Selective hydrogenation of cyclic ester to α, ω-diol catalyzed by cationic ruthenium complexes with trialkylphosphine ligands |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |