CN1049680C - Selective hydrogenation catalyst for alkyne in ethane-ethylene fraction - Google Patents
Selective hydrogenation catalyst for alkyne in ethane-ethylene fraction Download PDFInfo
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Abstract
The present invention provides a honeycombed palladium metal catalyst for removing alkyne through the selective hydrogenation of acetylene hydrocarbon in an ethane-ethene fraction. In the catalyst, alkali metals and(or) alkaline earth metals are adopted as auxiliary agents, a main framework is composed of a honeycomb-shaped material with axially parallel pore canals, and the pore number is from 200 to 400 pores/inch<2>. The specific surface area of the catalyst containing 0.01 to 0.8 wt% of palladium is from 5 to 120 m<2>/g. The present invention has the advantages of high selectivity of generated ethene, and small generating quantity of green oil. The catalyst can reduce the content of 0.3 to 3.5% of the acetylene hydrocarbon in the ethane-ethene fraction to below 2 ppm.
Description
The present invention relates to the selective acetylene hydrocarbon hydrogenation catalyst in a kind of ethane-ethylene fraction, more specifically say so a kind of contain basic metal and (or) alkaline-earth metal makes the cellular metallic palladium hydrogenation catalyst of auxiliary agent.
Now prove, (being lower than 1.40V%) pellet type catalyst (comprising sphere, bar shaped, cylindricality, annular, trilobal or quatrefoil) had hydrogenation selectivity preferably when alkynes content was relatively low in ethane-ethylene fraction, and alkynes content meets the requirements in the hydrogenated products; When alkynes content is higher relatively in ethane-ethylene fraction (meeting or exceeding 1.40V%), the result of use of pellet type catalyst then can not be satisfactory.Though, the alkynes that is lower than 2.5V% in ethane-ethylene fraction all can be eliminated through operation conditions optimization.But the hydrogenation process green oil generating amount obviously increases, and causes the catalyzer frequent regeneration, has reduced work-ing life; For the ethane-ethylene fraction of alkynes content greater than 2.5V%, the result of use of pellet type catalyst is more undesirable, and this is the structural limitations of pellet type catalyst own.Therefore seek a kind of catalyzer that is suitable for handling high alkynes content alkene fraction and seem very necessary.
United States Patent (USP) 3,489,809 disclose a kind of honeycombed catalyzer, and it can be reduced to the acetylene content of (1-3) V% in the ethylene gas below the 10ppm.This catalyzer is a carrier with the honeycombed pottery, and active constituent is palladium or palladium and promoter metal, and these assistant packet belong to and comprise rhodium, zirconium, gold and silver, copper and iron.Active constituent content is total carried catalyst weight (0.01～10) %, and wherein the content of promoter metal is (0.001～5) % of spendable palladium weight.Use temperature (180～200) ℃, air speed 50,000～4,000,000h
-1, linear velocity is (0.5～50) meter per second.Simultaneously, this patent also discloses a kind of multistage hydrogenation technique that uses this catalyzer, in what the acetylene hydrogenation technology in front, adopt this patent honeycomb type palladium metal catalyst that the acetylene content of (1～3) V% in the ethylene gas is reduced to 0.5%, in the end one-level is removed and is adopted existing pellet type catalyst acetylene content to be reduced to below the 10ppm in the alkynes technology again, and promptly two kinds of catalyzer are used.
The advantage that the objective of the invention is to comprehensive pellet type catalyst and existing honeycombed catalyzer, a kind of novel honeycomb palladium metal catalyst is provided, uses separately, the alkynes content of (0.3～3.5) V% in ethane-ethylene fraction can be reduced to below the 2ppm, the selectivity height, green oil generating amount is few.
Palladium content is (0.01～0.8) wt% in the honeycomb catalyst of the present invention, adopt basic metal and (or) alkaline-earth metal makes auxiliary agent, main body framework is by having the axially parallel duct, hole count be the cellular material formation of (200～400) hole/in2.Basic metal wherein can be Li, Na, K, Rb, Cs, preferably Li, Na, K; Alkaline-earth metal can be Be, Mg, Ca, Sr, Ba, preferably Mg, Ca, Ba.The adding of this auxiliary agent has improved selectivity of catalyst on the one hand, reduced the growing amount of green oil in the hydrogenation process on the other hand, but its add-on has remarkably influenced to the performance of catalyzer of the present invention, as when basic metal add-on during greater than 15wt%, this catalyst activity obviously descends, when alkaline-earth metal add-on during greater than 10wt%, this catalyst stability variation.Therefore, alkali metal content is lower than 15wt% in the honeycomb catalyst of the present invention, is preferably lower than 10wt%, and alkaline earth metal content is lower than 10wt%, is preferably lower than 8wt%.
Catalyzer of the present invention adopts general preparation method's preparation.
The skeleton raw material of honeycomb catalyst of the present invention is selected from aluminum oxide, silicon oxide, titanium oxide, magnesium oxide, aluminum oxide silicon monoxide, aluminum oxide titanium monoxide, aluminum oxide one magnesium oxide, silicon oxide titanium monoxide, silicon oxide one magnesium oxide, pottery etc., trichroite is preferably made the carrier that the sol solutions of coating refractory inorganic oxide behind the cellular skeleton is made catalyzer of the present invention.Refractory inorganic oxide can be aluminum oxide, silicon oxide, aluminum oxide carbon monoxide, accounts for 5～50% of vehicle weight, preferably 5～30%, the additive alkali metal and (or) alkaline-earth metal can add according to a conventional method.As: add during the carrier moulding, add when dip-coating aluminium colloidal sol, silicon sol, aluminium colloidal sol one silicon sol, add during the dipping active constituent.
With the nest honeybee carrier of moulding, seasoning behind coated with aluminum colloidal sol, silicon sol or aluminium colloidal sol one silicon sol, again in baking oven 105 ℃～200 ℃ dry 2～8 hours down, 500 ℃ then～1000 ℃ following roastings 2～10 hours.The surplus liquid of the dip-coating first time is repeated above-mentioned steps carries out dip-coating second time, after the seasoning again in 120 ℃～180 ℃ dryings 2～8 hours down, 600 ℃ then～1150 ℃ following roastings 2～10 hours.The palladium chloride aqueous solution of the certain density pH value 3～5 of final impregnating, after the seasoning in 105 ℃～200 ℃ dry 2～8 hours down, honeycomb palladium metal catalyst of the present invention is made in 400～800 ℃ of following roastings 2～12 hours.Specific surface is (5 ℃ 120) rice
2/ gram.
All need be before honeycomb catalyst of the present invention uses with hydrogen 120～250 ℃ of reduction 4～8 hours down, go out hydrogen in the reactor with nitrogen replacement then.
Honeycomb catalyst of the present invention is used to contain the industrial ethane-ethylene fraction of (0.3～3.5) V% alkynes and selects acetylene hydrogenation.When being less than 0.8V%, adopt alkynes content single-stage to remove alkynes technology; Alkynes content adopts in (0.8～1.6) V% scope the time secondary to remove alkynes technology; When alkynes content is higher than 1.6V%, adopt three grades and remove alkynes formula technology.The process operation parameter that adopts is as follows:
Temperature in (℃) 30～50
Reaction pressure (MPa) 2.1～2.6
Air speed (h
-1) 2000～22000
Hydrogen alkynes is than (volume ratio) 0.8～2.5: 1
Honeycomb catalyst of the present invention because adopt basic metal and (or) alkaline-earth metal makes auxiliary agent, thereby selectivity height, green oil generating amount are few, adopt single-stage or the multistage alkynes technology of removing (0.3～3.5) V% alkynes content in ethane-ethylene fraction can be reduced to below the 2ppm,
Embodiment 1
With commodity cordierite honeycomb material is matrix, behind the coated with aluminum colloidal sol, is immersed in pH and is in 2～5 the palladium chloride aqueous solution, makes the catalyzer that consists of the Pd/k trichroite after drying, the roasting, and palladium content is 0.04wt%, 17 meter 2/ gram of specific surface.Being used for alkynes content is ethane-ethylene fraction selection acetylene hydrogenation of 0.3V%.43 ℃ of temperature ins, air speed 3500h
-1, hydrogen alkynes is than (volume ratio) 1.8～2.0: 1.Select hydrogenation to the results are shown in table 1
Table 1
| Alkali metal content (wt%) | Acetylene content in the product, ppm | The ethane increment, % | Green oil generating amount, ppm |
| 0.06 3.0 7.8 | ≤1 ≤1 ≤2 | 0.20 0.23 0.41 | 23.4 30.8 83.7 |
Embodiment 2
K in embodiment 1 catalyzer is replaced with Ba, make the catalyzer that consists of the Pd/Ba/ trichroite, palladium content is 0.042wt%, 80.9 meters of specific surfaces
2/ gram.Being used for the ethane that alkynes content is 1.5V%---ethylene fraction is selected hydrogenation, adopts secondary to remove alkynes technology.And to control a conversion of alkyne be 60～70%.One 34 ℃, two 42 ℃ of temperature ins, 8000h of air speed
-1, two beds 6000h
-1, hydrogen alkynes is than (volume ratio) one 0.8～1.0: 1, two 1.2～1.4: 1.Select hydrogenation to the results are shown in table 2.
Table 2
| Alkaline earth metal content (wt%) | Acetylene content in the product, ppm | The ethane increment, % | Green oil generating amount, ppm |
| 0.01 3.0 6.5 | ≤2 ≤2 ≤2 | 0.83 0.96 1.01 | 64.1 66.7 83.6 |
Embodiment 3
K in embodiment 1 catalyzer is replaced with K-Ba, make the catalyzer that consists of the Pd/K-Ba/ trichroite, palladium content is 0.04wt%, 120 meters of specific surfaces
2/ gram.Being used for the ethane that alkynes content is 2.8V%---ethylene fraction is selected hydrogenation, adopts three grades to remove alkynes technology.Controlling a conversion of alkyne is 35～45%, and controlling two transformation efficiencys is 40～50%, one 30 ℃, two 46 ℃, three 46 ℃ of temperature ins, 10000h of air speed
-1, two beds 7000h
-1, three beds 3500h
-1, hydrogen alkynes is than (volume ratio) one 0.8～1.0: 1, two 1.2～1.4: 1, three 1.8～2.0: 1.Select hydrogenation to the results are shown in table 3.
Table 3
| Basic metal and alkaline earth metal content (wt%) | Acetylene content in the product, ppm | The ethane increment, % | Green oil generating amount, ppm |
| K-0.001 Ba-6.5 K-7.8 Ba-0.001 K-3.5 Ba-3.0 | ≤1 ≤2 ≤2 | 1.45 2.0 1.6 | 43.3 69.1 33.3 |
Comparative example 1
Selecting commodity cordierite honeycomb material for use is matrix, behind the coated with aluminum colloidal sol, being immersed in pH and being in 2～5 the palladium chloride aqueous solution, make the catalyzer of the Pd/ trichroite that does not contain any auxiliary agent after drying, the roasting, be used for the ethane that alkynes content is 2.8V%---ethylene fraction is selected acetylene hydrogenation.Adopt three grades to remove alkynes technology.All the other select hydrogenation to the results are shown in table 4 with embodiment three.
Table 4
| Palladium content (wt%) in the catalyzer | Acetylene content in the product, ppm | The ethane increment, % | Green oil generating amount, ppm |
| 0.04 0.15 0.8 | ≤2 ≤1 ≤1 | 2.05 2.23 2.59 | 89.9 80.3 96.7 |
Comparative example 2
The ethane that comparative example 1 catalyzer is used to contain 1.5V% alkynes---ethylene fraction is selected acetylene hydrogenation, adopts secondary to remove alkynes technology.All the other select hydrogenation to the results are shown in table 5 with embodiment two.
Table 5
| Palladium content (wt%) in the catalyzer | Acetylene content in the product, ppm | The ethane increment, % | Green oil generating amount, ppm |
| 0.04 0.15 0.8 | ≤2 ≤1 ≤1 | 0.3 0.6 1.2 | 45.5 57.1 77.2 |
Comparative example 3
Adopt commodity beaded catalyst C
31-1A is the comparative catalyst.This catalyst activity component is a palladium, and carrier is Al
2O
3, being used to contain the ethane of about 2.5V% alkynes alkane---ethylene fraction is selected acetylene hydrogenation, adopts three grades except that alkynes technology.Controlling a conversion of alkyne is that 35～45%, two transformation efficiencys are 40-45%.One 46 ℃, two 46 ℃, three 60 ℃ of temperature ins, 6500h of air speed
-1, two beds 4600h
-1, three beds 3000h
-1, hydrogen alkynes is than (volume ratio) 1.0-1.2: 1, two 1.4～1.6: 1, three 1.8～2.0: 1.Select hydrogenation to the results are shown in table 6.
Table 6
| Catalyzer | Acetylene content in the product, ppm | The ethane increment, % | Green oil generating amount, ppm |
| C 31-1A | ＜2 | 2.5 | 369.1 |
Comparative example 4
Adopting commodity beaded catalysts (G-58C) is the comparative catalyst.Being used to contain the ethane of about 2.5V% alkynes---ethylene fraction is selected acetylene hydrogenation, adopts three grades to remove alkynes technology.Controlling a conversion of alkyne is 35～45%, and controlling two transformation efficiencys is 40～45%.One 40 ℃, two 46 ℃, three 50 ℃ of temperature ins, 6000h of air speed
-1, two beds 4000h
-1, three beds 2500h
-1, hydrogen alkynes is than (volume ratio) one 1.0～1.2: 1, two 1.2～1.4: 1, three 1.8～2.0: 1.Select hydrogenation to the results are shown in table 7.
Table 7
| Catalyzer | Acetylene content in the product, ppm | The ethane increment, % | Green oil generating amount, ppm |
| G-58C | ＜2 | 2.0 | 211.9 |
Claims (9)
1. one kind is used for the honeycomb catalyst that ethane-ethylene fraction selective acetylene hydrocarbon hydrogenation removes alkynes, carrier framework is made of the cellular material with axially parallel duct, constitute carrier coated with refractory inorganic oxide again, active constituent is a palladium metal, it is characterized in that this catalyzer adopts basic metal or alkaline-earth metal to make auxiliary agent.
2. one kind is used for the honeycomb catalyst that ethane-ethylene fraction selective acetylene hydrocarbon hydrogenation removes alkynes, carrier framework is made of the cellular material with axially parallel duct, constitute carrier coated with refractory inorganic oxide again, active constituent is a palladium metal, it is characterized in that this catalyzer adopts basic metal and alkaline-earth metal to make auxiliary agent.
3. honeycomb catalyst according to claim 1 and 2 is characterized in that metallic palladium content is 0.01～0.8wt%.
4. honeycomb catalyst according to claim 1 and 2 is characterized in that described basic metal is K.
5. honeycomb catalyst according to claim 1 and 2 is characterized in that described alkaline-earth metal is Ba.
6. honeycomb catalyst according to claim 1 and 2 is characterized in that specific surface is 5～120 meters
2/ gram.
7. honeycomb catalyst according to claim 1 and 2 is characterized in that K content is 0.001～10wt%.
8. honeycomb catalyst according to claim 1 and 2 is characterized in that Ba content is 0.001～8wt%.
9. honeycomb catalyst according to claim 1 and 2 is characterized in that refractory inorganic oxide accounts for 5～30% of vehicle weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97118733A CN1049680C (en) | 1997-09-23 | 1997-09-23 | Selective hydrogenation catalyst for alkyne in ethane-ethylene fraction |
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|---|---|---|---|
| CN97118733A CN1049680C (en) | 1997-09-23 | 1997-09-23 | Selective hydrogenation catalyst for alkyne in ethane-ethylene fraction |
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| CN1176291A CN1176291A (en) | 1998-03-18 |
| CN1049680C true CN1049680C (en) | 2000-02-23 |
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| CN97118733A Expired - Fee Related CN1049680C (en) | 1997-09-23 | 1997-09-23 | Selective hydrogenation catalyst for alkyne in ethane-ethylene fraction |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1081666C (en) * | 1998-07-17 | 2002-03-27 | 中国石化齐鲁石油化工公司 | Selective hydrogen catalyst having catalysis and fractional distillation functions |
| CN1097480C (en) * | 1999-06-25 | 2003-01-01 | 中国石油化工集团公司 | Catalyst for selective hydrogenation of acetylene hydrocarbon |
| CN1090997C (en) * | 2000-04-30 | 2002-09-18 | 中国石油化工集团公司 | Selective hydrogenation acetylene-removing multimetal catalyst |
| CN106928008B (en) * | 2015-12-31 | 2019-11-08 | 中国石油天然气股份有限公司 | A kind of front-end hydrogenation of methanol-to-olefins product removes alkynes method |
| CN106927993B (en) * | 2015-12-31 | 2019-09-03 | 中国石油天然气股份有限公司 | A kind of method that methanol-to-olefins product front-end hydrogenation removes alkynes |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3489809A (en) * | 1968-04-17 | 1970-01-13 | Engelhard Min & Chem | Selective hydrogenation with a catalyst on a honeycomb support |
| CN85106117A (en) * | 1985-08-16 | 1986-10-29 | 化学工业部北京化工研究院 | The catalysis selective hydrogenation of alkynes and diolefine in the monoolefine |
| CN1071443A (en) * | 1991-10-04 | 1993-04-28 | 兰州化学工业公司化工研究院 | A kind of catalyzer that is used for one-stage selective hydrogenation of gasoline splitting |
| US5422329A (en) * | 1992-04-08 | 1995-06-06 | Hoechst Ag | Supported catalyst, process for its preparation and its use for the preparation of vinyl acetate |
| US5466652A (en) * | 1994-02-22 | 1995-11-14 | The Standard Oil Co. | Process for the preparation of vinyl acetate catalyst |
| CN1121501A (en) * | 1994-06-09 | 1996-05-01 | 法国石油公司 | Method for adding hydrogen with catalysis and catalyst which can be used in same |
-
1997
- 1997-09-23 CN CN97118733A patent/CN1049680C/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3489809A (en) * | 1968-04-17 | 1970-01-13 | Engelhard Min & Chem | Selective hydrogenation with a catalyst on a honeycomb support |
| CN85106117A (en) * | 1985-08-16 | 1986-10-29 | 化学工业部北京化工研究院 | The catalysis selective hydrogenation of alkynes and diolefine in the monoolefine |
| CN1071443A (en) * | 1991-10-04 | 1993-04-28 | 兰州化学工业公司化工研究院 | A kind of catalyzer that is used for one-stage selective hydrogenation of gasoline splitting |
| US5422329A (en) * | 1992-04-08 | 1995-06-06 | Hoechst Ag | Supported catalyst, process for its preparation and its use for the preparation of vinyl acetate |
| US5466652A (en) * | 1994-02-22 | 1995-11-14 | The Standard Oil Co. | Process for the preparation of vinyl acetate catalyst |
| CN1121501A (en) * | 1994-06-09 | 1996-05-01 | 法国石油公司 | Method for adding hydrogen with catalysis and catalyst which can be used in same |
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| CN1176291A (en) | 1998-03-18 |
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