CN102911714B - Selective hydrogenation method for C5 fraction of ethylene cracking by-product - Google Patents
Selective hydrogenation method for C5 fraction of ethylene cracking by-product Download PDFInfo
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Abstract
The invention discloses a selective hydrogenation method for C5 fraction of an ethylene cracking by-product. The selective hydrogenation method comprises the following steps of (1) performing selective hydrogenation by using the C5 fraction of the ethylene cracking by-product as a raw material to remove alkadiene and alkyne, wherein catalyst is arranged in 3-5 reaction sections along flow direction of reaction materials; catalyst volume content in each reaction section is increased by 5-30% than that in the former adjacent reaction section successively; the amount of the catalyst in a first section is 8%-20% of a total volume of the catalyst; and the amount of the catalyst in last section is 40%-65% of the total volume of the catalyst; (2) adding a diluent in the raw material, wherein the diluent is a saturated alkane; and (3) adding a polymerization inhibitor selectively in the raw material. The method can remove alkadiene and alkyne from the C5 fraction with high content of alkadiene and alkyne via selective hydrogenation, simultaneously solves the easy coking problem of the catalyst, and can guarantee that a reaction apparatus runs stably for a long time.
Description
Technical field
The invention belongs to chemical field, relate to a kind of light oil selective hydrogenation and prepare the method for ethylene cracking material except diolefine and alkynes, especially with cracking of ethylene C
5for reaction raw materials, diolefine is wherein carried out to the method that ethylene cracking material is prepared in selective hydrogenation processing.
Background technology
For the raw material of steam cracking or catalytic pyrolysis preparing ethylene, although for many years, the formation of world Ethylene raw material is basicly stable, and always take petroleum naphtha and lighter hydrocarbons as main, but in recent years, due to the difference of various countries' resource, the variation of raw materials market, there is the trend to diversified development in ethylene raw.Such as after liquefied gas hydrogenation, be used as ethylene cracking material etc.The C of cracking of ethylene by product
5cut can be used as ethylene raw by two step hydrogenation, i.e. the first step cracking of ethylene C
5removing alkadiene by selective hydrogenation and alkynes; Second step, makes it to be converted into alkane as ethylene cracking material using its monoolefin hydrogenation.
CN101428228 discloses a kind of selective hydrogenation catalyst and preparation method thereof, but the method is only suitable in C
4the selective hydrogenation of cut.CN1145891A discloses a kind of method of hydrotreating, and the method is raw materials used for taking out the C after remaining
5cut, wherein monoolefine content is high, and diene content is very low, only has 1.5%, and this method is only applicable to C
5cut one step Hydrogenation pentane.CA1410515A discloses a kind of selective hydrogenation catalyst and preparation method thereof and at C
5application in cut.But this patent has only been introduced catalyzer alkynes is had to good selective hydrogenation activity, do not introduce the content of diolefine and alkynes in raw material, and in raw material, the number of the content of diolefine and alkynes there is very large difference to the requirement of technique and catalyzer.
CN101429453A provides a kind of pyrolysis gasoline cut fraction section to select the method for hydrogenation except diolefine.Although the method is better except diolefine to selecting hydrogenation, the method is that full-cut fraction pyrolysis gasoline is selected to the method for hydrogenation except diolefine, and the method reaction pressure is also higher in addition.CN1631526 discloses a kind of method for removing alkadiene by selective hydrogenation, but in this patent, only relates to a kind of manufacture method of catalyzer.CN1676581 discloses a kind of method for removing alkadiene by selective hydrogenation, but the method temperature of reaction is higher.
Disclosed method for removing alkadiene by selective hydrogenation is all not suitable for the C of cracking of ethylene by product above
5cut removing alkadiene by selective hydrogenation and alkynes are prepared ethylene cracking material.Mainly the problem of existence is, cracking of ethylene by product C
5the diolefine of cut and alkynes content are higher, and in hydrogenation process, these materials are easy to green coke, and thermal discharge therefore, need to find a kind of suitable technique and realize cracking of ethylene C
5selective hydrogenation and removing diolefine and alkynes, make ethylene cracking material for its follow-up deep hydrogenation technical support be provided, and only in this way could effectively expand cracking of ethylene C
5range of application.
Summary of the invention
For the deficiencies in the prior art, the one that provides of the present invention is with cracking of ethylene C
5cut is the C of the cracking of ethylene by product that raw material, particularly diolefine and alkynes content are high
5cut is raw material, carries out the method for selective hydrogenation and removing diolefine and alkynes; Solved cracking of ethylene C simultaneously
5the problems such as in raw material, diene content is high, the easy coking of catalyzer.
Cracking of ethylene by product C of the present invention
5cut process for selective hydrogenation comprises following content:
(1) with cracking of ethylene by product C
5cut is raw material, carry out selective hydrogenation and removing diolefine and alkynes, catalyzer arranges 3 ~ 5 conversion zones, along the mobile direction of reaction mass, each reacting section catalyst volumetric usage increases by 5 ~ 30 percentage points than an adjacent upper reacting section catalyst volume successively, the consumption of the first reacting section catalyst is 8% ~ 20% of catalyzer cumulative volume, and the consumption of most end reacting section catalyst is 40% ~ 65% of catalyzer cumulative volume, and each reacting section catalyst volume percent sum is 100%;
(2) in raw material, add thinner, thinner is alkane;
(3) in raw material, selectivity adds stopper.
In the methods of the invention, reaction temperature in is 20 ~ 120 ℃, is preferably 40 ~ 90 ℃; Reaction pressure is 0.04 ~ 8MPa, is preferably 1.0 ~ 6.0MPa; Volume space velocity (C when stock liquid
5the volume space velocity of cut charging) be 0.4 ~ 25h
-1, be preferably 1 ~ 5h
-1; Hydrogen to oil volume ratio (hydrogen and C under import standard state
5the volume ratio of feedstock) be 200:1 ~ 1500:1, be preferably 300:1 ~ 1000:1.The hot(test)-spot temperature of each conversion zone is lower than 120 ℃, preferably lower than 110 ℃.
In the inventive method, reactor inlet temperature, in the time of 20 ℃ ~ 39 ℃, can not need to add stopper in raw material; , in raw material, add stopper when reaction the temperature in >=40 ℃.Described stopper is to react the material that has inhibition to diolefine and alkynes hot polymerization, can be: one or more in Resorcinol, para benzoquinone, p-ten.-butylcatechol, methylene blue etc.The inventive method is preferably tert-butyl catechol.The add-on of stopper in reaction system is 5 × 10
-3~ 5 × 10
-1mg/m
3, be preferably 1 × 10
-2~ 1 × 10
-1mg/m
3.
In the inventive method, described thinner is alkane or mixed alkanes, is specially C5 alkane or boiling point alkane or the mixed alkanes within the scope of 90 ℃-180 ℃.Thinner recycles (using alkane or the mixed alkanes of boiling point within the scope of 90 ℃-180 ℃ is thinner) after can separating with reaction product, also can not separate common further use (using C5 alkane is thinner) with reaction product.The alkane of thinner can be paraffinic hydrocarbons or naphthenic hydrocarbon, and thinner can derive from the further hydrogenation of product that the inventive method obtains by product saturated monoolefine, can be also alkane or the naphthenic hydrocarbon in other source.While recycling after thinner need to separate with reaction product, the boiling point of thinner will be higher than raw material C
5the boiling point of cut, preferably the two boiling-point difference is greater than 30 ℃, and boiling-point difference is preferably 50 ℃ ~ 150 ℃, makes thinner and reacted C
5cut easily adopts vacuum flashing to separate.Thinner is specifically preferably heptane, octane or cracking of ethylene C
5the product of cut gained after two-stage hydrogenation is saturated etc.
In the inventive method, raw material C
5the volume ratio of cut and thinner is 1:1 ~ 1:10, is preferably 1:2 ~ 1:5.
In the inventive method, the noble metal hydrogenation catalyst for refining that the catalyzer that each conversion zone uses is this area routine, generally take aluminum oxide as carrier, take palladium and/or platinum as active ingredient, by weight, the content of active ingredient in catalyzer is 0.2% ~ 6%, and catalyzer can use commercially available prod, also can prepare by this area ordinary method.
In the inventive method, cracking of ethylene by product C
5the diolefine of feedstock and the content of alkynes are higher, and run-of-the-mill percentage composition can be greater than 3%, conventionally can be greater than 5.0%.
Find through large quantity research, at cracking of ethylene by product C
5cut carries out in selective hydrogenation process, and reaction has following features:
(1) known according to reaction kinetics result of study, this exothermic heat of reaction is inhomogeneous, in the time that reaction mass passes through catalyst bed reaction, at reaction bed entrance, be reaction time in 1/4 of the whole residence time ~ 1/3 o'clock, exothermic heat of reaction amount has just reached 70% ~ 80% of whole reaction heat.
(2) the easy polymerization reaction take place of diolefine and alkynes, particularly under comparatively high temps, polyreaction is faster, so this reaction is adapted at carrying out under low temperature, liquid-phase condition hydrogenation reaction.Adopt palladium series catalyst, C
5in the time of 28 ℃ of temperature >, just can there is hydrogenation reaction in diolefine, 2-butyne.For diene content higher (being greater than 5.0%), lower (the < 2mg/M of sulphur content
3) cracking of ethylene C
5cut material, its hydrogenation process is applicable to selecting palladium catalyst.
(3) at cracking of ethylene by product C
5in cut, work as C
5when diolefine and 2-butyne sum total content reach 5.0%, temperature reaches 100 ℃ just can there is hot polymerization reaction; When higher than 120 ℃, the reaction of diolefine hot polymerization can obviously be accelerated, especially cyclopentadiene.Based on this, for the diene content cracking of ethylene C of higher (being greater than 5.0%)
5hydrogenation reaction, for avoiding C wherein
5diolefine reacts with 2-butyne generation hot polymerization, at the residing concrete reaction environment of differential responses section, just requires the hot(test)-spot temperature of its reaction bed lower than 120 ℃, preferably lower than 110 ℃ according to reaction mass.
(4) for this reaction, although select platinum and/or palladium catalyst can guarantee that the starting point temperature of reaction is lower, but also to consider constraint condition given in actual production: first, the raw material of being sent here by upstream device under normal circumstances, its temperature is 45 ℃ of left and right, although the catalyst activity at 28 ℃ just can meet the requirement of this reaction, consider the problem of energy consumption, the reaction temperature in being of practical significance generally fixes on more than 45 ℃ or 45 ℃; The second, catalyzer has normal use temperature scope, and the in the initial stage of that temperature in is low, and latter stage, temperature in was high, and for common platinum and/or palladium catalyst, according to result of study, its, temperature in fixed on 90 ℃ of left and right in latter stage.
(5) according to the character of reaction mass, consider the impact of hydrogen, the hot(test)-spot temperature of reaction is answered 100 ℃ of <, reaction pressure requires > 1.0MPa the most suitable, under this state, reaction raw materials can be remained to liquid phase, be conducive to reduce the generation of polymerization and coking reaction.
(6) 100 ℃ of conditions of reaction hot(test)-spot temperature < to be met, the method for charging dilution can be adopted.
(7) thinner is selected C5 alkane or alkane or the mixed alkanes of boiling point within the scope of 90 ℃-180 ℃, because the boiling point of main ingredient in raw material is all below 50 ℃, the two boiling-point difference is greater than 40 ℃, and selected thinner is also alkane, the two can not do clear cutting apart, reacted like this C
5just can adopt vacuum flashing to separate with thinner.
the critical temperature of table 1 related substances.
| Title | Critical temperature Tc (℃) |
| 3-methyl-1-butene | 177 |
| Iso-pentane | 187 |
| Isosorbide-5-Nitrae-pentadiene | 205 |
| 2-butyne | 215 |
| 1-amylene | 190 |
| 2-methyl-1-butene alkene | 192 |
| Skellysolve A | 196 |
| Trans-2-amylene | 202 |
| Cis-2-amylene | 203 |
| 2-methyl-2-butene | 197 |
the each component vapour pressure of table 2 reaction product (atm).
| Temperature, ℃ | 20 | 60 | 100 | 140 | Emergent pressure |
| 3-methyl-1-butene | 0.998 | 3.441 | 8.905 | 19.11 | 34.7 |
| Iso-pentane | 0.756 | 2.699 | 7.155 | 15.59 | 33.37 |
| Isosorbide-5-Nitrae-pentadiene | 0.806 | 2.742 | 6.925 | 14.47 | 37.4 |
| 2-butyne | 0.769 | 2.804 | 7.460 | 16.20 | 50.20 |
| 1-amylene | 0.698 | 2.647 | 7.415 | 16.85 | 40.0 |
| 2-methyl-1-butene alkene | 0.666 | 2.456 | 6.639 | 14.68 | 34.0 |
| Skellysolve A | 0.559 | 2.114 | 5.180 | 13.02 | 33.25 |
| Trans-2-amylene | 0.549 | 2.108 | 5.869 | 13.24 | 36.1 |
| Cis-2-amylene | 0.537 | 2.067 | 5.764 | 13.02 | 36.0 |
| 2-methyl-2-butene | 0.769 | 1.974 | 5.674 | 13.07 | 34.0 |
For above-mentioned research, for cracking of ethylene C
5the content higher (quality percentage composition is greater than 5.0%) of middle diolefine, sulphur content are lower (lower than 2 mg/M
3) cracking of ethylene C
5fraction hydrotreating method, the present invention proposes suitable treatment process.
The present invention is by further investigation cracking of ethylene C
5the various response characteristics of selective hydrogenation and removing diolefine and alkynes process, propose above-mentioned hydroprocessing process.Proposed by the invention: (1) catalyzer dilutes filling, can reduce hot(test)-spot temperature, even up thermometer bulb, can effectively control occur in hydrogenation process large at reaction bed ingress thermal discharge, cause the too high problem of reaction bed ingress temperature rise, avoid the catalyzer first contacting with material to cause coking because containing in charging compared with high diolefine, affected the problem of integer catalyzer life cycle.(2) charging adopts dilution process, can improve the linear velocity of reactant, is conducive to shift out fast reaction heat, can reduce reaction bed average reaction temperature and realize making full use of of integer catalyzer, has extended the running period of catalyzer.(3) thinner is selected the saturated alkane of 90 ℃-180 ℃ of boiling points, and the two boiling-point difference is large, and the two can not do clear cutting apart, and adopts vacuum flashing to separate, and method is simple.(4) when reaction temperature in is greater than after 40 ℃, in raw material, add stopper, solve the problem of diolefine and alkynes easy polymerization under high reaction temperature, alleviate widely and caused reaction bed ingress coking speed because of polyreaction, reaction bed resistance increment problem faster, also solve because of it simultaneously and caused the production equipment decoking of often stopping work, the problem that can not steadily produce for a long time.
Embodiment
Further illustrate the solution of the present invention and effect below by embodiment.
The LHC1-01 hydrogenation catalyst that the catalyzer using in embodiment is Fushun Petrochemical Research Institute's development and production, the use of can regenerating.Physico-chemical property is as table 3.
the physico-chemical property of table 3 hydrogenation catalyst.
| Catalyzer | LHC1-01 |
| Active metal, quality % | 0.3 ± 0.01 (in Pd) |
| Crushing strength, N/cm | ≮100 |
| Tap density, g/cm 3 | 0.55~0.62 |
| Shape | Trifolium |
| Size, mm | Φ3×(3~8) |
Embodiment 1 ~ embodiment 7
Reaction used catalyst is LHC1-01; Reactor is adiabatic reactor.For making reaction bed temperature even, catalyzer adopts segmentation dilution filling.By reactant flow direction, embodiment 1～4 every section of catalyst volume consumption is followed successively by: 15%, 30%, 55%, and loaded catalyst is 100ml; Embodiment 5～7 every section of catalyst volume consumptions are followed successively by: 10%, 15%, 25%, 50%, and loaded catalyst is 100ml.Reaction raw materials is the C in ethylene production
5raffinate, thinner and C
5the two ratio is C
5: the volume ratio=1:2 of thinner; C
5raffinate forms in table 4.Reaction is upper feeding, and reaction mass flows out from reactor bottom, enters in gas-liquid separator after cooling, tail gas is discharged from separator top, bottom liquid phases timing sampling, with gas chromatographic analysis composition, the concrete reaction conditions of embodiment 1 ~ embodiment 7 and the results are shown in table 5.
table 4 C
5
raffinate composition.
| Composition | mol% |
| Total carbon four hydrocarbon | 3.01 |
| 3-methyl-1-butene | 1.51 |
| Iso-pentane | 13.56 |
| Isosorbide-5-Nitrae-pentadiene | 7.53 |
| 2-butyne | 1.93 |
| 1-amylene | 9.43 |
| 2-methyl-1-butene alkene | 11.88 |
| Skellysolve A | 25.67 |
| Isoprene | 0.45 |
| Trans-2-amylene | 5.28 |
| Cis-2-amylene | 2.87 |
| 2-methyl-2-butene | 2.90 |
| Trans-1,3-pentadiene | 0.02 |
| Cyclopentadiene | 0.20 |
| Cis-1,3-pentadiene | 0.02 |
| Cyclopentenes | 0.00 |
| Pentamethylene | 0.52 |
| Other carbon five | 0.11 |
| Total carbon six | 12.47 |
| Benzene | 0.39 |
| Toluene | 0.23 |
| Other dimers | 0.02 |
| Alkyl norbornylene | 0.01 |
| Dicyclopentadiene | 0.01 |
| The above heavy constituent of carbon ten | 0.01 |
| Amount to | 100 |
| Diolefin | About 10%(mol%) |
| Basic nitrogen | ≤40μg/g |
reaction result under table 5-1 operation condition and different temperature in.
| ? | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| Numbering | LHC1-6-6 | LHC1-5-1 | LHC1-4-2 | LHC1-5-4 |
| Temperature in, ℃ | 29 | 30 | 35 | 40 |
| Reaction bed hot(test)-spot temperature, ℃ | 50 | 53 | 56 | 62 |
| Reaction pressure, MPa | 1.7 | 1.7 | 1.7 | 1.7 |
| Volume space velocity, h -1 | 1.0 | 1.8 | 1.0 | 1.0 |
| Import hydrogen to oil volume ratio | 600:1 | 300:1 | 500:1 | 400:1 |
| C 5Diene content, mol% | 0 | 0 | 0 | 0 |
| Alkynes content, mol% | 0.07 | 0.04 | 0.03 | 0.04 |
| Stopper, mg/m 3 | / | / | / | 0.5×10 -2 |
| Thinner | C 5Mixed alkanes | Normal heptane | Octane | Nonane |
reaction result under table 5-2 operation condition and different temperature in.
| ? | Embodiment 5 | Embodiment 6 | Embodiment 7 |
| Numbering | LHC1-11-1 | LHC1-12-3 | LHC1-13-1 |
| Temperature in, ℃ | 60 | 70 | 80 |
| Reaction bed hot(test)-spot temperature, ℃ | 83 | 92 | 102 |
| Reaction pressure, MPa | 1.7 | 1.7 | 1.8 |
| Volume space velocity, h -1 | 1.0 | 1.0 | 1.2 |
| Import hydrogen to oil volume ratio | 200:1 | 600:1 | 600:1 |
| C 5Diene content, mol% | 0 | 0 | 0 |
| Alkynes content, mol% | 0 | 0 | 0 |
| Stopper, mg/m 3 | 1×10 -2 | 2×10 -2 | 5×10 -2 |
| Thinner | Decane | Hexanaphthene | Methylcyclohexane |
Embodiment 8
A catalyzer will have industrial application value, except will having good transformation efficiency and selectivity, also will possess satisfactory stability simultaneously.Reaction used catalyst is LHC1-01; Reaction process is adiabatic reactor.For making reaction bed temperature even, catalyzer adopts segmentation dilution filling.By reactant flow direction, every section of catalyst volume consumption is followed successively by: 10%, 15%, 25%, 50%, and loaded catalyst is 100ml.Reaction raw materials is C
5raffinate, thinner and C
5the two ratio is C
5: thinner=1:2; C
5raffinate forms with the table 4 in embodiment 1.Reaction is for upper feeding, and reaction mass flows out from reactor bottom, enters in gas-liquid separator after cooling, and tail gas is discharged from separator top, and bottom liquid phases timing sampling forms with gas chromatographic analysis.At reaction pressure 1.7MPa, Reactor inlet hydrogen/oily 600:1(v), liquid air speed 1.0h
-1under condition, carried out the life experiment of 1000h, its experiment the results are shown in Table 6.
the longevity test of table 6 catalyzer.
| Runtime/h | Temperature in/℃ | Diene content mol % | Alkynes content mol % |
| 100 | 40 | 0 | 0 |
| 200 | 40 | 0 | 0 |
| 300 | 40 | 0 | 0 |
| 400 | 42 | 0 | 0.03 |
| 500 | 42 | 0 | 0 |
| 600 | 42 | 0 | 0.03 |
| 700 | 44 | 0 | 0 |
| 800 | 44 | 0 | 0 |
| 900 | 44 | 0 | 0 |
| 1000 | 44 | 0 | 0 |
As shown in Table 6, this catalyzer this catalyzer in the time of 1000h end-of-life also has good activity and selectivity.According to similar catalyst running experience, can estimate that this Catalyst running single pass life can reach more than 1 year.
Embodiment 9
Reaction used catalyst is LHC1-01; Reaction process is adiabatic reactor.For making reaction bed temperature even, catalyzer adopts segmentation dilution filling.By reactant flow direction, every section of catalyst volume consumption is followed successively by: 10%, 15%, 25%, 50%, and loaded catalyst is 100ml.Reaction raw materials is the C that dicyclopentadiene content is high
5raw material, thinner and C
5the two ratio is C
5: thinner=1:5; Raw material forms in table 7, and thinner is C
5mixed alkanes.Reaction is for upper feeding, and reaction mass flows out from reactor bottom, enters in gas-liquid separator after cooling, and tail gas is discharged from separator top, bottom liquid phases timing sampling, and with gas chromatographic analysis composition, concrete reaction conditions and the results are shown in table 8.
table 7 dicyclopentadiene content is highc
5 raw material composition.
| Density (30 ℃), g/cm 3 | 0.945 |
| Viscosity (30 ℃), cp | 4.9 |
| Boiling range, ℃ | ? |
| IBP/10% | 46/90 |
| 30%/50% | 142/150 |
| 70%/90% | 157/164 |
| 95%/EBP | 165/168 |
| S，mg/kg | 93.4 |
| Basic nitrogen, mg/kg | 47.2 |
| Chromatogram composition, quality % | ? |
| Paraffinic hydrocarbons+naphthenic hydrocarbon | 6.25 |
| Alkene | 78.31 |
| Aromatic hydrocarbons | 3.76 |
reaction result under table 8 operation condition and different temperature in.
| Numbering | LHC1-17-1 |
| Temperature in, ℃ | 50 |
| Hot(test)-spot temperature, ℃ | 100 |
| Reaction pressure, MPa | 5.0 |
| Volume space velocity is (to C 5Raw material) ,/h -1 | 1.0 |
| Reactor inlet hydrogen to oil volume ratio is (to C 5Raw material) | 600:1 |
| C 5Diene content, mol% | 0.86 |
| Alkynes content, mol% | 0 |
Note: in reaction product, diolefine and alkynes content summation are less than 1% for the control index of hydrogenation reaction.
Claims (8)
1. a cracking of ethylene by product C
5cut process for selective hydrogenation, is characterized in that comprising following content:
(1) with cracking of ethylene by product C
5cut is raw material, carry out selective hydrogenation and removing diolefine and alkynes, catalyzer arranges 3 ~ 5 conversion zones, along the mobile direction of reaction mass, each reacting section catalyst volumetric usage increases by 5 ~ 30 percentage points than an adjacent upper reacting section catalyst volume successively, the consumption of the first reacting section catalyst is 8% ~ 20% of catalyzer cumulative volume, and the consumption of most end reacting section catalyst is 40% ~ 65% of catalyzer cumulative volume, and each reacting section catalyst volume percent sum is 100%;
(2) in raw material, add thinner, thinner is alkane;
(3) in raw material, selectivity adds stopper, and stopper is one or more in Resorcinol, para benzoquinone, p-ten.-butylcatechol, methylene blue;
The catalyzer that each conversion zone uses is noble metal hydrogenation catalyst for refining, and noble metal hydrogenation catalyst for refining is take aluminum oxide as carrier, and take palladium and/or platinum as active ingredient, by weight, the content of active ingredient in catalyzer is 0.2% ~ 6%;
Reaction temperature in is 20 ~ 120 ℃, and reaction pressure is 0.04 ~ 8MPa, and when stock liquid, volume space velocity is 0.4 ~ 25h
-1, hydrogen to oil volume ratio is 200:1 ~ 1500:1, the hot(test)-spot temperature of each conversion zone is lower than 120 ℃.
2. in accordance with the method for claim 1, it is characterized in that: reaction temperature in is 40 ~ 90 ℃, and reaction pressure is 1.0 ~ 6.0MPa, and when stock liquid, volume space velocity is 1 ~ 5h
-1, hydrogen to oil volume ratio is 300:1 ~ 1000:1, the hot(test)-spot temperature of each conversion zone is lower than 110 ℃.
3. according to the method described in claim 1 or 2, it is characterized in that:, add stopper in raw material, the add-on of stopper in reaction system is 5 × 10 when reaction the temperature in>=40 ℃
-3~ 5 × 10
-1mg/m
3.
4. it is characterized in that in accordance with the method for claim 1: described thinner is C5 alkane or the alkane of boiling point within the scope of 90 ℃-180 ℃.
5. according to the method described in claim 1 or 4, it is characterized in that: thinner recycles after separating with reaction product, or thinner does not separate common further use with reaction product.
6. according to the method described in claim 1 or 4, it is characterized in that: raw material C
5the volume ratio of cut and thinner is 1:1 ~ 1:10.
7. according to the method described in claim 1 or 4, it is characterized in that: raw material C
5the volume ratio of cut and thinner is 1:2 ~ 1:5.
8. it is characterized in that in accordance with the method for claim 1: cracking of ethylene by product C
5the quality percentage composition of the diolefine of feedstock and alkynes is greater than 3%.
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| BE756546A (en) * | 1969-09-23 | 1971-03-23 | British Petroleum Co | IMPROVEMENTS RELATED TO THE HYDROGENATION OF UNSATURATED ESSENCES |
| FR2553760B1 (en) * | 1983-10-25 | 1986-05-02 | Inst Francais Du Petrole | PROCESS FOR SELECTIVE HYDROGENATION IN THE PRESENCE OF SOLVENT OF ACETYLENIC COMPOUNDS OF A BUTADIAN RICH C4 HYDROCARBON CUT |
| CN1005268B (en) * | 1985-08-16 | 1989-09-27 | 化学工业部北京化工研究院 | Catalytic selective hydrogenation of alkynes and dialkenes in mono-alkenes |
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