CN104557392B - A kind of production method of pentane - Google Patents
A kind of production method of pentane Download PDFInfo
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- CN104557392B CN104557392B CN201310471720.1A CN201310471720A CN104557392B CN 104557392 B CN104557392 B CN 104557392B CN 201310471720 A CN201310471720 A CN 201310471720A CN 104557392 B CN104557392 B CN 104557392B
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Abstract
The invention discloses a kind of production method of pentane, light dydrocarbon is raw material using after ether for it, and hydrogenated and removing residual olefin produces the pentane product that penta bromine index is qualified.Specific steps include:1)Hydrogenation reaction is carried out by fixed bed catalyst bed after light dydrocarbon and hydrogen mixing after ether, the weight percentage that catalyst is Ni in Ni/ diatomite catalyst, catalyst is 10~50%;2) hydrogenation products at a temperature of 10~40 DEG C by storng-acid cation exchange resin fixed bed to remove remaining unsaturated hydrocarbons.Low raw-material cost that the present invention is used, production method technique is simple and energy consumption is relatively low, and the obtained bromine index of pentane penta is qualified.
Description
Technical field
The invention belongs to chemosynthesis technical field, and in particular to a kind of production method of pentane.
Background technology
Pentane is generally the mixture of isopentane and pentane, and it is quite varied in the purposes of chemical field.Pentane can use
Make a kind of preferable polystyrene material foaming agent;Simultaneously because any destruction is not present to atmospheric ozone layer in pentane, it can use
In replacement freon.In addition, pentane is also used as molecular sieve desorbing agent, industrial solvent, extractant and industrial chemicals etc..
In the prior art, pentane is generally refined using the lighter hydrocarbons of the saturated alkane containing C4~C6 and formed, and these lighter hydrocarbons include
Condensate, light naphthar and direct steaming gasoline etc..But because condensate and light naphthar composition are complicated, rectifying separation is difficult, and
Unsaturated hydrocarbons is remained in final products more.When separating pentane by raw material of direct steaming gasoline, due to general direct steaming gasoline hydrogenation
Not fully, the pentane product that bromine index is 100 or so can only be equally produced, this will influence its performance.Steamed in naphtha
The a considerable amount of C 5 fractions of by-product during vapour cracking ethylene preparation, the comprehensive utilization of current C 5 fraction most worthy is logical
Cross separation of extractive distillation and produce the higher pentadiene of wherein economic value, three kinds of diolefins of isoprene and dicyclopentadiene.
During C 5 fraction separation of extractive distillation diolefin, some light dydrocarbon feed separation for containing iso-amylene comes out, this portion
Divide material to account for 25wt% of C 5 fraction total amount or so, this material is generally industrially referred to as coarse isoamylene fraction, it is raw
Produce the raw material of iso-amylene product.At present tert amyl methyl ether(TAME) cracking process using most iso-amylene production methods, i.e., thick isoamyl
Alkene fraction and methanol reaction generation tert amyl methyl ether(TAME), are then refining to obtain high-purity methyl tert-amyl ether, then Pintsch process is obtained
Obtain iso-amylene.When producing iso-amylene, simply by the 2-methyl-1-butene alkene and 2- methyl-2-butenes and first of coarse isoamylene fraction
Alcohol is etherified, and the other monoolefines and alkane separated are commonly referred to as light dydrocarbon after ether, is mainly used as fuel, typically not work
Work is utilized.
Chinese patent ZL200410018519.9 provides a kind of presence of lightweight C 5 fraction in Ni/ diatomite catalyst
Under the hydrogenated reaction method for preparing pentane.It by hydrogenation products by removing remaining unsaturation by granular carclazyte fixed bed
The method of hydrocarbon produces qualified pentane product.But because granular carclazyte activity is relatively low, 150~170 DEG C need to be up in temperature
Under conditions of remove a small amount of alkene, energy consumption is higher.
The content of the invention
The invention provides a kind of production method of pentane, the technical problems to be solved by the invention are to provide a kind of technique
Simply, energy consumption is relatively low, light dydrocarbon after ether is hydrogenated and removing residual olefin produces the qualified pentane product of penta bromine index
Method.
The following is specific technical scheme of the invention:
A kind of production method of pentane, this method comprises the following steps successively:
1)Hydrogenation reaction is carried out by fixed bed catalyst bed after light dydrocarbon and hydrogen mixing after ether.Volume liquid hourly space velocity (LHSV) control
It is made as 1.0~5.0hr-1, system pressure control is 1.0~4.0MPa, and reaction-ure feeding temperature control is 20~100 DEG C., hydrogen
Molar ratio with unsaturated hydrocarbons total amount in light dydrocarbon after ether is(2~5)∶1.Catalyst be Ni/ diatomite catalyst, its be with
Ni is active constituent, using diatomite as the loaded catalyst of carrier, and Ni weight percentage is 10~50% in catalyst.
Hydrogenation reaction product part is returned as solvent, and the charged material weight ratio of light dydrocarbon and solvent is 1 after ether:(6~10).
2)Hydrogenation products are at a temperature of 10~40 DEG C by storng-acid cation exchange resin fixed bed to remove remnants
Unsaturated hydrocarbons, the volume liquid hourly space velocity (LHSV) control of material is 1.0~5.0hr-1, system pressure control is 0.1~0.8MPa, enters material temperature
Spend for 10~40 DEG C.
Above-mentioned steps 1)Described in volume liquid hourly space velocity (LHSV) preferably control as 1.5~3.0hr-1;System pressure is preferably controlled
For 1.5~3.0MPa;Reaction-ure feeding temperature is preferably controlled as 30~60 DEG C;Hydrogen and unsaturated hydrocarbons total amount in light dydrocarbon after ether
Molar ratio is preferably(3~4)∶1;The charged material weight ratio preferably 1 of light dydrocarbon and solvent after ether:(7~9).
Step 1)The Ni/ diatomite catalyst used is classical hydrogenation of unsaturated hydrocarbons catalyst, and catalyst can be using normal
Prepared by the infusion process of rule, diatomite first is configured into particle is made carrier, and then being impregnated with the solution containing Ni salt will
Ni is loaded on carrier, then finished catalyst is made through drying, high-temperature roasting, reduction treatment and sieving.This catalyst is present
Two kinds of hydrogenation activities position, wherein high activity position can be catalyzed the hydrogenation of monoolefine, and middle low activity position can be catalyzed diolefin or alkynes
The hydrogenation of hydrogenation and part monoolefine.After usual ether it is C 5 hydrogenated after, its mono-olefin content is about 0.05%, in theory accordingly
Bromine index is 133mgBromine/100gOil, it is impossible to reach as EPS foaming agents≤100mgBromine/100gThe requirement of oil.
Inventor is found through experiments that monoolefine remaining in light dydrocarbon after ether is 2- methyl-2-butenes after hydrogenation, and it is carbon
Composition the most difficult is hydrogenated with five alkene, but can be seen that 2- methyl-2-butenes from its structure has active double bond again,
Therefore the characteristics of can occurring oligomerisation reaction on storng-acid cation exchange resin surface using 2- methyl-2-butenes, makes 2- first
Base -2- butencs are dimer, it is possible to achieve C 5 monoolefin content after ether after reduction hydrogenation, and then reduce its bromine index
Purpose.
Advantages of the present invention is very notable compared with prior art, because storng-acid cation exchange resin has highly acid
Sulfonate functional groups, it can effectively after catalytic hydrogenation ether in light dydrocarbon monoolefine oligomerisation reaction so that reaction can be normal
Temperature is lower to be carried out, and not only simplifies handling process, and energy consumption can be greatly reduced, and reduces processing cost.Penta bromine index≤
100mgBromine/100gThe qualified pentane product of oil.
Embodiment
Below by specific embodiment, the invention will be further described, due to relative to prior art, invention
The improvement for focusing on removing monoolefine step, remaining is essentially identical with prior art, therefore embodiment will focus on remaining to removing
The description of monoolefine step.In embodiment, the definition such as volume liquid hourly space velocity (LHSV), bromine index of pentane product is respectively:
The milligram number of bromine index=100 gram supplies consumption bromine
Wherein, mono-olefin content is measured by gas chromatography in material, and bromine index uses titration measuring, bromine index
The content of unsaturated double-bond in product is directly reacted.
Raw material sources:
(1)Storng-acid cation exchange resin is purchased from Shandong Qilu Keli Chemical Research Institute Co., Ltd., trade name
QRE-01 resin catalysts.The physical index of table 1QRE-01 catalyst
The physical index of table 1QRE-01 catalyst
Project | Unit | Index |
Color and shape | It is dark-grey to taupe spherolite | |
Water content | % | 48~52 |
Weight exchange capacity | mmol·g -1 | ≥5.0 |
Wet true density(20℃) | g/ml | 1.20~1.30 |
Wet apparent density | g/ml | 0.75~0.85 |
Average pore radius | nm | 20~60 |
Specific surface area | m2·g -1 | ≥40 |
Specific pore volume | 0.25~0.50 | |
Granularity(0.35~1.2mm) | % | ≥95 |
Wear-resisting rate | % | ≥95 |
Heap density(Butt, water content 5~10%) | g/ml | 0.62~0.67 |
Tripe is swelled in methanol(Butt, water content 5~10%) | % | 30~40 |
Dispatch from the factory pattern | Hydrogen |
(2)Ni/ diatomite catalyst is prepared using conventional infusion process, and diatomite first is configured into particle is made load
Body, is then impregnated with the solution containing Ni salt, Ni is loaded on carrier, then through drying, high-temperature roasting, reduction treatment and sieving
Finished catalyst is made.
【Embodiment 1~17】
Hydrogenation reactor is one100ml Ni/ are loaded in 25mm × 1000mm stainless steel tubular reactor, reaction tube
Diatomite catalyst, catalyst is by active constituent of Ni, Al2O3With SiO2Mixture be carrier, Ni contents be 10~
50wt%.Reactor bottom loads inert ceramic balls.After C 5 fraction material is preheated after ether with pump with the speed that sets by top
Hydrogenation reactor is sent into, hydrogen is entered in reactor by gas distributor, and C 5 fraction material mixes laggard with hydrogen after ether
Enter beds and carry out hydrogenation reaction.Hydrogenation material enters a gas-liquid separator by hydrogenation reactor bottom, by gas-liquid separation
Emptied after entering wet-test meter metering after the adjusted valve decompression of unreacting hydrogen that device is separated, or Returning reacting system after compression,
Liquid phase material is used after being down to room temperature as deolefination raw material.Deolefination reactor is one25mm × 1000mm's is stainless
Load 100ml strong acid cation exchange resin catalysts in steel pipe type reactor, reaction tube, system pressure control for 0.1~
0.8MPa;The composition of C 5 fraction material is shown in Table 2 after ether.
Hydroconversion condition and deolefination condition are shown in Table 3, and table 4 is data after processing.
Table 2
Component | Content(wt)% |
Dimethyl ether | 0.58 |
3- methyl butenes -1 | 0.13 |
Isopentane | 16.25 |
1,4- pentadienes | 0.53 |
1- amylenes | 11.34 |
2-methyl-1-butene alkene | 0.45 |
Pentane | 50.58 |
The anti-amylenes of 2- | 9.84 |
2- is along amylene | 5.55 |
2- methyl-2-butenes | 2.79 |
Other light dydrocarbons | 1.96 |
Table 3
Table 4
Claims (2)
1. a kind of production method of pentane, it is characterised in that comprise the following steps that:
1)Hydrogenation reaction is carried out by fixed bed catalyst bed after light dydrocarbon and hydrogen mixing after ether;Volume liquid hourly space velocity (LHSV) is controlled
1.0~5.0hr-1, system pressure control is 1.0~4.0MPa, and reaction-ure feeding temperature control is 20~100 DEG C, hydrogen and ether
The molar ratio of light dydrocarbon unsaturated hydrocarbons total amount is afterwards(2~5): 1, catalyst is Ni in Ni/ diatomite catalyst, catalyst
Weight percentage be 10~50%, hydrogenation reaction product part is returned as solvent, the weight that feeds intake of light dydrocarbon and solvent after ether
Amount is than being 1:(6~10);
2)Hydrogenation products are at a temperature of 10~40 DEG C by storng-acid cation exchange resin fixed bed to remove remaining insatiable hunger
And hydrocarbon, the volume liquid hourly space velocity (LHSV) control of material is 1.0~5.0hr-1, system pressure control is 0.1~0.8MPa, and feeding temperature is
10~40 DEG C.
2. production method according to claim 1, it is characterised in that:Step 1)Described in product liquid hourly space velocity (LHSV) control be 1.5
~3.0hr-1;System pressure control is 1.5~3.0MPa;Reaction-ure feeding temperature control is 30~60 DEG C;Hydrogen and carbon after ether
The molar ratio of unsaturated hydrocarbons total amount is in five(3~4)∶1;The charged material weight ratio of light dydrocarbon and solvent is 1 after ether:(7~9).
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