CN1207254C - Method for preparing pentane by using hydrogenation on distillation of petroleum carbon five - Google Patents
Method for preparing pentane by using hydrogenation on distillation of petroleum carbon five Download PDFInfo
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- CN1207254C CN1207254C CN 02145057 CN02145057A CN1207254C CN 1207254 C CN1207254 C CN 1207254C CN 02145057 CN02145057 CN 02145057 CN 02145057 A CN02145057 A CN 02145057A CN 1207254 C CN1207254 C CN 1207254C
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Abstract
The present invention relates to a method for preparing pentane by hydrogenating petroleum C5 fractions. In the method, extracted C5 obtained by extracting diolefin hydrocarbons and separating isoamylene with a tert-amyl methyl ether cracking method is used as a raw material; under the action of a catalyst, high-purity pentane is obtained by hydrogenation; the reaction temperature is from 40 to 300 DEG C; the reaction pressure is from 0 to 5MPa; the liquid hourly space velocity of the C5 raw material is from 0.3 to 10 hr<-1>; the molar charging ratio of hydrogen to C5 is 0.7 to 8.0; Al2O3 is used as a carrier of the catalyst; active components contain Pd and a component A, wherein A is selected from one of Mo, Cu or Zn, or the mixture of two of Mo, Cu and Zn. Pd/Al2O3 of the catalyst used in the present invention is modified by using proper non noble metal. On the premise of high Pd/Al2O3 catalyst activity and mild technological conditions, the depth of hydrogenation reaction is increased, and the intoxication caused by oxygen-containing group impurities is avoided.
Description
Technical field
The present invention relates to the method for unsaturated hydrocarbons, particularly contain the method for the Petrocarbon 5 distillate hydrogenation preparing pentane of unsaturated hydrocarbons by hydrogenation preparing alkane.
Background technology
The a considerable amount of C 5 fractions of by-product in the process of petroleum cracking system ethene, it is the effective way that improves the ethylene production economic benefit that C 5 fraction is fully utilized.At present, the comprehensive utilization of C 5 fraction mainly is to carry out carbon five separation, obtains diolefin and the higher isopentene of using value such as isoprene, m-pentadiene.Owing to contain the very approaching compound of many boiling points in the C 5 fraction, isopentene therefrom to be separated with general separation method and to be difficult for, it is the tert amyl methyl ether(TAME) cracking process that present people adopt maximum separation methods, be that C 5 fraction generates tert amyl methyl ether(TAME) with the methyl alcohol reaction earlier, and then through Pintsch process, contain isopentene in the split product, methyl alcohol and small amount of impurities, remove methyl alcohol through water elution, and can make the high purity isopentene through rectifying.Extracting diolefin and the raffinate carbon-5 material that adopts above-mentioned tert amyl methyl ether(TAME) cracking process to separate isopentene can be used as oil fuel and use, but obviously the higher utilization of economic benefit is that it is carried out deep processing again, for example can make pentane by hydrogenation.Pentane is a kind of important basic chemical industry raw material, can be used for producing amylalcohol, valeral etc., and the whipping agent and the extraction agent that can be used as macromolecular material, also can be used as green refrigerant replacement fluorine Leon, it still is a kind of good organic solvent simultaneously.
Chinese patent ZL95111774.2 had once proposed a kind of similar C 5 fraction to be prepared the method for pentane by catalyst hydrogenation, and wherein the activity of such catalysts component is base metal elements such as precious metals such as Pd, Pt, or Cu, Co, Ni, Mo or Fe.This method is that to prepare pentane be unusual ideal to raw material with the C 5 fraction without tert amyl methyl ether(TAME) cracking process extracting isopentene, but owing to contain trace impurities such as water, methyl alcohol, tert amyl methyl ether(TAME), dme in the C 5 fraction behind tert amyl methyl ether(TAME) cracking process extracting isopentene, though these oxy radical impurity content are very low, but can cause poisoning to noble metal catalyst especially Pd, even can make catalyst deactivation at short notice.Though adopt non-precious metal catalyst not have the problem of poisoning of catalyst, the yield of pentane is relatively low, and reaction conditions is more harsh.
Summary of the invention
The invention provides a kind of method of Petrocarbon 5 distillate hydrogenation preparing pentane, its technical problem to be solved be can be with extracting diolefin and separated the raffinate carbon-5 that obtains behind the isopentene through the tert amyl methyl ether(TAME) cracking process and make highly purified pentane by hydrogenation reaction as raw material, the catalyzer that is adopted requires to be difficult for being poisoned by oxy radical, and have higher pentane yield, thereby overcome the defective that prior art exists.
Below be the technical scheme that the present invention solves the problems of the technologies described above:
A kind of method of Petrocarbon 5 distillate hydrogenation preparing pentane, this method with extracting diolefin and to have separated the raffinate carbon-5 that obtains behind the isopentene through the tert amyl methyl ether(TAME) cracking process be raw material, carbon Wuyuan material hydrogenation in the presence of catalyzer obtains high-purity pentane, temperature of reaction is 40～300 ℃, reaction pressure is 0～5MPa, and the liquid hourly space velocity of carbon Wuyuan material is 0.3～10hr
-1, the molar feed ratio of hydrogen and carbon five is 0.7～8.0, catalyzer is with Al
2O
3Be carrier, contain Pd and component A in the activity group component of load, A takes from one or more the mixture among Mo, Cu or the Zn, and the content of Pd is 0.1～1.0wt% in the catalyzer, and the content of component A is 0.5～1.8wt%.
Above-mentioned activity of such catalysts component A is preferably Mo, the content of active constituent Pd is preferably 0.2～0.4wt%, the content of active component A is preferably 0.8～1.0wt%, though along with the content increase reactive behavior of Pd can improve, can reduce economy when surpassing 1.0wt%; Temperature of reaction is preferably 100～150 ℃; Reaction pressure is preferably 0.5～2.0MPa; The liquid hourly space velocity of carbon Wuyuan material is 1.0～5.0hr
-1The molar feed ratio of hydrogen and carbon five is preferably 1.0～5.0.
Essence of the present invention be the catalyzer that adopts with suitable base metal to Pd/Al
2O
3Carry out modification, guaranteeing Pd/Al
2O
3Under the prerequisite of catalyst activity height, processing condition gentleness, increased the degree of depth of carrying out of hydrogenation reaction.The contriver finds also that by a large amount of experiments the noble metal catalyst after the modification can be avoided being poisoned by oxy radical impurity.
Catalyzer adopts the known pickling process in present technique field to prepare, and following preparation process only is that the contriver recommends:
At first, with median size be about 3mm, specific surface area is 160～220m
2The spherical alumina carrier of/g is dried in 120 ℃～200 ℃ temperature range, flood by several times by equi-volume impregnating then, the different activities component is loaded on the carrier, at last through super-dry and roasting, make active constituent after reaching suitable distribution on the carrier, promptly get the catalyzer finished product.The water miscible salt of the general employing of the raw material of each active ingredient.
Hydrogenation process of the present invention is 40～300 ℃ in temperature of reaction, and reaction pressure is 0～5MPa, and the liquid hourly space velocity of carbon Wuyuan material is 0.3～10hr
-1, the molar feed ratio of hydrogen and carbon five is that 0.7～8.0 processing condition scope all is feasible.But wherein temperature of reaction is preferably 100 ℃～150 ℃, temperature is crossed low olefin conversion and is decreased, though higher temperature of reaction can improve reactive behavior, further improve olefin conversion, but being higher than the probability that produces isomerization side reaction after 150 ℃, temperature increases, though olefin conversion is very high, the pentane yield is on a declining curve.The optimum range of reaction pressure is 0.5～2.0MPa, when pressure is lower than 0.5MPa, causes the vaporization of carbon five components easily, moves hot speed and reduces, and the beds temperature rise is excessive, can increase the probability of occurrence of side reaction equally.And after pressure surpasses 2.0MPa, olefin conversion and pentane yield will slow down with the trend that pressure increases, and too high reaction pressure will make the economy decline of device.Preferable liquid hourly space velocity scope is 1.0～5.0hr
-1, low excessively liquid hourly space velocity is favourable to improving olefin conversion, but the treatment capacity of device is too low, and liquid hourly space velocity is higher than 5hr
-1The time, the olefin conversion downward trend is apparent in view.The optimum range of hydrogen and C 5 fraction molar ratio is 1.0～5.0, and hydrogen and C 5 fraction mol ratio are lower than at 1.0 o'clock, and olefin conversion is low excessively, and hydrogen and C 5 fraction mol ratio are higher than at 5.0 o'clock, and the trend that transformation efficiency improves is slowed down.
Compared with prior art, the invention has the advantages that can be with extracting diolefin and separated the raffinate carbon-5 that obtains behind the isopentene through the tert amyl methyl ether(TAME) cracking process and make highly purified pentane by hydrogenation reaction as raw material, olefin conversion, pentane yield are all up to more than 99%.In addition, the hydrogenation reaction processing condition are also relatively gentleer.
Embodiment
In an embodiment, the definition of olefin conversion, pentane yield is respectively:
Diolefin has been expected for extracting and has separated the raffinate carbon-5 that obtains behind the isopentene through the tert amyl methyl ether(TAME) cracking process that it consists of in the carbon Wuyuan that embodiment adopts:
Amylene-1 (wt%) 10.89
Along amylene-2 (wt%) 28.96
Anti-amylene-2 (wt%) 14.09
Rare-2 (wt%) 4.27 of 2-methyl fourth
Trimethylammonium butene-1 (wt%) 0.065
Cyclopentenes (wt%) 0.023
1,4-pentadiene (wt%) 0.31
Iso-pentane (wt%) 3.19
Skellysolve A (wt%) 38.03
Water (ppm) 250～300
Methyl alcohol (ppm) 150～200
Ethers impurity (ppm) 200～300
One, Preparation of catalysts:
[embodiment 1]
With median size is that 3mm, specific surface area are 160～220m
2The spherical alumina carrier of/g places in the baking oven, and temperature is set at 150 ℃, keeps 5 hours, then cool to room temperature in dry environment.
It is in Palladous chloride-dilute solution of sodium hydroxide of 1.25wt% that above-mentioned dried alumina supporter is put into 40g Palladous chloride concentration, floods in high temperature air dry 2～3 hours then 15～20 hours.Again this carrier being dropped into 60g concentration is to flood 15～20 hours in the 27wt% amine molybdate solution.With load the carrier of active constituent 2～3 hours in 120 ℃ of down dry backs in 400 ℃ of roasting temperatures.
The catalyst activity component that obtains is: palladium: 0.3wt%, molybdenum: 0.8wt%.
[embodiment 2]
With the amine molybdate solution among the mixed aqueous solution replacement embodiment 1 of 29wt% amine molybdate and 2wt% cupric nitrate, all the other are with embodiment 1.
The catalyst activity component that obtains is: palladium: 0.3wt%, molybdenum: 0.9wt%, copper 0.02wt%.
[embodiment 3]
With concentration is the amine molybdate solution of the mixed aqueous solution replacement embodiment 1 of 24wt% amine molybdate and 2wt% zinc nitrate, and all the other are with embodiment 1.
The catalyst activity component that obtains is: palladium: 0.3wt%, molybdenum: 0.7wt%, zinc: 0.05wt%.
[embodiment 4]
Change the palladium chloride aqueous solution concentration among the embodiment 1 into 0.9wt%, all the other are with embodiment 1.
The catalyst activity component that obtains is: palladium: 0.2wt%, molybdenum: 0.8wt%.
[embodiment 5]
Change the palladium chloride aqueous solution concentration among the embodiment 1 into 0.45wt%, all the other are with embodiment 1.
The catalyst activity component that obtains is: palladium: 0.1wt%, molybdenum: 0.8wt%.
[embodiment 6]
Change the palladium chloride aqueous solution concentration among the embodiment 1 into 1.8wt%, and with the amine molybdate solution among the mixed aqueous solution replacement embodiment 1 of 29wt% amine molybdate and 3wt% cupric nitrate, all the other are with embodiment 1.
The catalyst activity component that obtains is: palladium: 0.4wt%, molybdenum: 0.9wt%, copper: 0.05wt%.
[embodiment 7]
Proofing time and the dipping time during amine molybdate solution time of carrier among the embodiment 1 in palladium chloride solution all shortened to 10 hours, and all the other are with embodiment 1.
The catalyst activity component that obtains is: palladium: 0.3wt%, molybdenum: 0.8wt%.
Two, the hydrogenation of carbon Wuyuan material:
[embodiment 8～19]
Above-mentioned carbon Wuyuan material is mixed with the hydrogen of process metering through supercharging, metering back, enter hydrogenator.Mixture enters the high pressure separating tank and implements gas-liquid separation behind the hydrogenation after condensation.Gas phase after the separation (unreacting hydrogen) is discharged from high score jar top, and its velocity of discharge is controlled by system pressure, the emptying after the wet flow indicator metering of the gas after the discharge; Liquid phase material (pentane product) is discharged from high score jar bottom, and the velocity of discharge is controlled by high score jar liquid level.The pentane product of discharging enters the product jar.
The concrete processing condition that adopt of each embodiment see Table 1, and reaction result sees Table 2.
Table 2.
| Catalyzer (embodiment) | Pressure (MPa) | Temperature (℃) | Liquid hourly space velocity (hr -1) | Charge ratio (mol ratio) | |
| Embodiment 1 | 1 | 4.8 | 93 | 1 | 5 |
| Embodiment 2 | 1 | 2.0 | 90 | 1 | 7.8 |
| Embodiment 3 | 3 | 0.2 | 50 | 0.5 | 1.0 |
| Embodiment 4 | 6 | 1.0 | 110 | 1 | 0.7 |
| Embodiment 5 | 2 | 0.1 | 100 | 1 | 2.5 |
| Embodiment 6 | 5 | 1.8 | 95 | 1 | 4 |
| Embodiment 7 | 3 | 0.5 | 130 | 1 | 1.5 |
| Embodiment 8 | 4 | 0.8 | 145 | 1 | 3 |
| Embodiment 9 | 4 | 1.0 | 130 | 2 | 2.0 |
| Embodiment 10 | 1 | 1.5 | 190 | 4 | 2.5 |
| Embodiment 11 | 2 | 1.6 | 238 | 8 | 1.5 |
| Embodiment 12 | 7 | 1.2 | 170 | 3 | 0.8 |
Annotate: charge ratio is a hydrogen: carbon five
Table 3.
| Olefin conversion (%) | Pentane yield (%) | Pentane product purity (%) | |
| Embodiment 1 | 99.92 | 99.99 | 99.90 |
| Embodiment 2 | 99.89 | 99.99 | 99.88 |
| Embodiment 3 | 99.70 | 99.62 | 99.84 |
| Embodiment 4 | 99.34 | 98.80 | 99.52 |
| Embodiment 5 | 98.70 | 98.62 | 98.98 |
| Embodiment 6 | 99.90 | 99.96 | 99.83 |
| Embodiment 7 | 99.77 | 99.72 | 99.84 |
| Embodiment 8 | 99.88 | 99.88 | 99.88 |
| Embodiment 9 | 99.70 | 99.80 | 99.87 |
| Embodiment 10 | 99.48 | 99.10 | 99.63 |
| Embodiment 11 | 99.53 | 99.29 | 99.67 |
| Embodiment 12 | 99.54 | 99.52 | 99.69 |
Claims (8)
1, a kind of method of Petrocarbon 5 distillate hydrogenation preparing pentane, this method with extracting diolefin and to have separated the raffinate carbon-5 that obtains behind the isopentene through the tert amyl methyl ether(TAME) cracking process be raw material, carbon Wuyuan material hydrogenation in the presence of catalyzer obtains pentane, temperature of reaction is 40～300 ℃, reaction pressure is 0～5MPa, and the liquid hourly space velocity of carbon Wuyuan material is 0.3～10hr
-1, the molar feed ratio of hydrogen and carbon five is 0.7～8.0, catalyzer is with Al
2O
3Be carrier, contain Pd and component A in the active constituent of load, A takes from one or more the mixture among Mo, Cu or the Zn, and the content of Pd is 0.1～1.0wt% in the catalyzer, and the content of component A is 0.5～1.8wt%.
2, the method for preparing pentane according to claim 1 is characterized in that described activity of such catalysts component A is Mo.
3, the method for preparing pentane according to claim 1 and 2, the content that it is characterized in that described activity of such catalysts component Pd is 0.2～0.4wt%.
4, the method for preparing pentane according to claim 1 and 2, the content that it is characterized in that described activity of such catalysts component A is 0.8～1.0wt%.
5, the method for preparing pentane according to claim 1 is characterized in that described temperature of reaction is 100～150 ℃.
6, the method for preparing pentane according to claim 1 is characterized in that described reaction pressure is 0.5～2.0MPa.
7, the method for preparing pentane according to claim 1 is characterized in that the liquid hourly space velocity of described carbon Wuyuan material is 1.0～5.0hr
-1
8, the method for preparing pentane according to claim 1, the molar feed ratio that it is characterized in that described hydrogen and carbon five is 1.0～5.0.
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| Application Number | Priority Date | Filing Date | Title |
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| CN 02145057 CN1207254C (en) | 2002-11-05 | 2002-11-05 | Method for preparing pentane by using hydrogenation on distillation of petroleum carbon five |
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103012032A (en) * | 2011-09-28 | 2013-04-03 | 中国石油化工股份有限公司 | Method for preparing pentane by hydrogenating light C5 fractions |
| CN104557392B (en) * | 2013-10-11 | 2017-07-21 | 中国石油化工股份有限公司 | A kind of production method of pentane |
| CN107739290A (en) * | 2017-09-16 | 2018-02-27 | 濮阳市联众兴业化工有限公司 | A kind of method that cracking c_5 prepares pentane foaming agent |
| CN111099950B (en) * | 2018-10-25 | 2024-04-23 | 中国石油化工股份有限公司 | Method for improving conversion rate of carbon five fraction hydrogenation reaction based on molybdenum-nickel/aluminum oxide catalysis |
| CN112007626A (en) * | 2019-05-31 | 2020-12-01 | 中国石油化工股份有限公司 | Preparation method and application of alumina-titanium oxide composite carrier |
| CN112778073A (en) * | 2021-01-05 | 2021-05-11 | 中国神华煤制油化工有限公司 | Method for preparing pentane from coal-based mixed pentene and application thereof |
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Owner name: SHANGHAI PETROCHEMIAL CO LTD, CHINA PETROCHEMICAL Free format text: FORMER OWNER: SHANGHAI PETROCHEMIAL CO LTD, CHINA PETROCHEMICAL CORP Effective date: 20070615 |
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Effective date of registration: 20070615 Address after: 200540 Shanghai city Jinshan District Jin Road No. 48 Co-patentee after: CHINA PETROLEUM & CHEMICAL Corp. Patentee after: Sinopec Shangai Petrochemical Co.,Ltd. Address before: 200540 Shanghai city Jinshan District Jin Road No. 48 Patentee before: Sinopec Shangai Petrochemical Co.,Ltd. |
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