CN103787815B - A kind of method of hydrotreating of divinyl tail gas - Google Patents
A kind of method of hydrotreating of divinyl tail gas Download PDFInfo
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Abstract
The invention provides the method for hydrotreating that a kind of butadiene extraction unit is rich in alkynes tail gas.Butadiene Extraction tail gas, first carries out selective hydrogenation at one-stage hydrogenation reactor, is 1,3-butadiene by vinylacetylene hydrocracking wherein; One-stage hydrogenation reaction product is through being separated, be rich in 1, the part of 3-divinyl send butadiene extraction unit, rest part carries out selective hydrogenation again through second-stage hydrogenation reactor, alkynes wherein, diene hydrogenation are converted into 1-butylene, and secondary hydrogenation reaction product send 1-butylene retrieving arrangement.The method fully can reclaim the valuable material in divinyl tail gas, remarkable in economical benefits.
Description
Technical field
The present invention relates to petrochemical industry, particularly relate to the method for hydrotreating being rich in alkynes tail gas that a kind of butadiene extraction unit produces.
Background technology
1,3-butadiene in cracking c_4 cut is generally refined by the method for two sections of solvent extraction rectifying and conventional distillation, and this device produces the divinyl tail gas being rich in alkynes.In divinyl tail gas, alkyne concentration is higher, is generally greater than 20 % by weight, the highest more than 40 % by weight.These waste gas being rich in alkynes there is no industrial utility value at present, can only send torch burning process.Because high density alkynes is easily polymerized blast, therefore the raffinate of general employing containing butane, butylene send torch burning after diluting, and so just causes the very large wasting of resources.Along with the increasing of hydrocarbon vapours cracking severity in recent years, in cracking c_4, alkynes content is in rising trend, and the tail gas amount being rich in alkynes that butadiene extraction unit produces also increases considerably.If the tail gas these being rich in alkynes makes full use of, utilization ratio and the economic benefit of hydrocarbon resources greatly will be improved.
In prior art, divinyl tail gas adopts method of hydrotreating processing and utilization usually, can utilize the rich alkynes salvage stores that Butadiene Extraction produces.
Method be the hydrocarbon mixture being rich in alkynes that produces with butadiene extraction unit for a raw material, make hydrogen and alkynes even divinyl react to remove alkynes even divinyl, product can be used as fuel, also can reclaim 1-butylene and other monoolefine further.CN03159237.6 discloses the Application way being rich in the hydrocarbon mixture of alkynes that a kind of butadiene extraction unit produces, and hydrogen and alkynes even divinyl react to remove alkynes even divinyl.The first stage reactor of the method is heat-insulating bubbling bed reactor, and catalyzer is two-pack containing group VIII metal or multicomponent catalyst; Second stage reactor is heat-insulating bubbling bed reactor, and catalyzer is containing the catalyzer of group VIII metal as active ingredient.
In the method, the alkynes in tail gas and 1,3-butadiene are all hydrogenated to 1-butylene, are not recovered as important industrial chemicals 1,3-butadiene, and the economy that carbon four fully utilizes obviously reduces.
Another kind method carries out selec-tive hydrogenation to the divinyl tail gas being rich in alkynes, alkynes is converted into divinyl and monoolefine, then sends butadiene extraction unit back to, to reclaim divinyl wherein.CN200810239462.3 discloses the selec-tive hydrogenation method of the height unsaturated hydrocarbons in a kind of C-4-fraction, with the salvage stores being rich in alkynes obtained after Butadiene Extraction for raw material, in the presence of a catalyst, adopt fixed-bed reactor, selec-tive hydrogenation obtains 1,3-divinyl, then reaction product is sent back to extraction plant.The operational condition that hydrogenation technique adopts is: temperature of reaction is 30 ~ 90 DEG C, and reaction pressure is 1.0 ~ 4.0MPa, and liquid air speed is 7 ~ 20h
-1.Catalyzer take aluminum oxide as the palladium series catalyst of carrier, and specific surface area is 50 ~ 150m
2/ g, specific pore volume is 0.25 ~ 1.0ml/g.
As everyone knows, in the c4 fraction of high concentration ethylene ethyl-acetylene (VA), ethylacetylene (EA), divinyl, the activity of hydrogenation catalyst to VA is the highest, first carries out hydrogenation reaction to it, and after VA is almost completely by hydrogenation, EA just participates in hydrogenation reaction.If EA is also completely by hydrogenation, catalyzer just carries out hydrogenation to divinyl, causes a large amount of losses of divinyl.
In embodiment disclosed in CN200810239462.3 1 ~ 8, VA transformation efficiency is at 90 ~ 93%, EA transformation efficiency 100%, and the yield of 1,3-butadiene is greater than 100%, and the practical situation of this and prior art there are differences.Use prior art and catalyzer, when EA complete hydrogenation, divinyl loss is very large.As by VA complete hydrogenation, do not lose, then EA hydrogenation hardly if control 1,3-butadiene, in import and export material, the concentration of EA is almost constant.Due in divinyl tail gas, EA concentration is higher, therefore CN200810239462.3 patented technology is used, in guarantee 1, during the situation that 3-divinyl does not lose, in hydrogenation products, EA concentration is higher, and this material send butadiene extraction unit to make raw material, can be comparatively large to two extraction systematic influences, increase operational load and the energy consumption of tower.
Summary of the invention
In order to fully recycle divinyl tail gas, overcome in prior art and reclaim the higher problems such as comparatively large or 1,3-butadiene loss is larger to Butadiene Extraction systematic influence of EA concentration in 1,3-butadiene, with the problem such as 1-butylene output is not high, the invention provides a kind of divinyl tail gas hydrogenation method.
The method of hydrotreating of a kind of divinyl tail gas provided by the invention is achieved in that
A method of hydrotreating for divinyl tail gas, the method comprises the following steps successively:
(1) from the divinyl tail gas of butadiene extraction unit, post liquefaction with mix from the liquid phase of one-stage hydrogenation reactor outlet separating tank and a section feeding hydrogen after, enter one-stage hydrogenation reactor top, carry out selective hydrogenation reaction; Reaction product enters one-stage hydrogenation reaction outlet separating tank after cooling, the tank deck non-condensable gas carrying device that described one-stage hydrogenation reaction outlet separating tank obtains, liquid phase at the bottom of the tank obtained, a part is circulated to one-stage hydrogenation reactor inlet, and rest part enters butadiene recovery column;
Described one-stage hydrogenation reactor is heat-insulating fixed-bed reactor; The catalyzer of described selective hydrogenation reaction: to be selected from one or more in aluminum oxide, gac, carbon black, zeolite, molecular sieve, silicon oxide as carrier, take palladium as active ingredient, to be selected from one or more in Bi, Sb, Pb, In, the VIIIth race's element being different from palladium, IB race element, rare earth element, alkali metal, alkali earth metal, halogens for modified component; Described active ingredient accounts for 0.01 ~ 50% of described catalyst weight, and described modified component accounts for 0.1 ~ 20% of described catalyst weight;
The condition of described selective hydrogenation reaction is: reactor inlet temperature is 10 ~ 80 DEG C, and pressure is 1.0 ~ 3.0MPa, and in the mixture entering described hydrogenator, the mol ratio of hydrogen and vinylacetylene is 1 ~ 5, and recycle feed volume ratio is 10 ~ 30; Described recycle feed volume ratio is be circulated to the inventory of one-stage hydrogenation reactor inlet and the ratio of described post liquefaction divinyl tail gas inventory from described one-stage hydrogenation reaction outlet separating tank;
(2) from liquid phase rectifying in described butadiene recovery column of described one-stage hydrogenation reaction outlet separating tank; The top gaseous phase overhead product of described butadiene recovery column is after overcooling, gas-liquid separation, what obtain is main containing 1, the liquid phase material of 3-divinyl send butadiene extraction unit, the non-condensable gas discharger obtained, and the kettle material of described butadiene recovery column enters second-stage hydrogenation reactor after boosting;
The working pressure of described butadiene recovery column is 0.3 ~ 0.8MPa, and reflux ratio is 10 ~ 30;
(3) react after the liquid phase that exports separating tank and two section feeding hydrogen mix from kettle material and the secondary hydrogenation of described butadiene recovery column, enter second-stage hydrogenation reactor top, carry out hydrogenation reaction; Described hydrogenation reaction product enters described second-stage hydrogenation reactor outlet separating tank after being cooled to 30 ~ 50 DEG C, the tank deck non-condensable gas carrying device that described secondary hydrogenation reaction outlet separating tank obtains, liquid phase at the bottom of the tank obtained, a part is circulated to second-stage hydrogenation reactor entrance, and rest part send 1-butylene tripping device to reclaim 1-butylene;
Described second-stage hydrogenation reactor is heat-insulating fixed-bed reactor; The catalyzer of described hydrogenation reaction: take pseudo-boehmite as carrier; Containing nickel, molybdenum, zinc in catalyzer, described nickel account for total catalyst weight 10 ~ 40%, described molybdenum account for total catalyst weight 0.5 ~ 3%, described zinc accounts for 0.5 ~ 3% of total catalyst weight; Described catalyzer is also containing IA race element, and described IA race element accounts for 0.1 ~ 5% of total catalyst weight;
The condition of described hydrogenation reaction is: reactor inlet temperature is 10 ~ 80 DEG C, and pressure is 1.0 ~ 3.0MPa, and enter hydrogen and alkynes in the mixture of described hydrogenator, the mol ratio of diolefine is 1 ~ 5, recycle feed volume ratio is 20 ~ 60.
In the specific implementation, described divinyl tail gas contains: butane 0 ~ 5 % by weight, butylene 0 ~ 15 % by weight, divinyl 20 ~ 60 % by weight, ethylacetylene and vinylacetylene 20 ~ 50 % by weight.
In the specific implementation, in step (1), selective hydrogenation reaction can select hydrogenation catalyst well known in the prior art, such as selective acetylene hydrocarbon hydrogenation catalyst disclosed in CN102249838, CN102249834, catalyzer is using aluminum oxide as carrier, take palladium as active ingredient, with Ag, Mg, K for modified component; Described active component palladium accounts for 0.1 ~ 10% of described catalyst weight, and described modified component Ag, Mg, K account for 0.01 ~ 10%, 0.01 ~ 5%, 0.01 ~ 2% of described catalyst weight; Described in preferred catalyzer, active component palladium accounts for 2 ~ 4% of described catalyst weight, and described modified component Ag, Mg, K account for 1 ~ 2%, 1 ~ 3%, 0.03 ~ 1% of described catalyst weight.
The condition of described selective hydrogenation reaction is: reactor inlet temperature is 30 ~ 60 DEG C, pressure is 1.2 ~ 2.0MPa, preferably 35 ~ 50 DEG C, 1.4 ~ 1.6MPa; For ensureing that catalyzer has good selectivity, control and reduce the reaction of 1,3-butadiene and hydrogen, hydrogen: the mol ratio of vinylacetylene controls 1 ~ 1.5, preferably 1 ~ 1.2; Due in first stage reactor, vinylacetylene per pass conversion is not high, and recycle stock can control on the one hand the temperature rise of reactor, and can improve the total transformation efficiency of vinylacetylene on the other hand, recycle ratio is 15 ~ 25, and preferably 17 ~ 23.
Generate 1,3-butadiene at one-stage hydrogenation reactor medium vinyl acetylene selective hydrogenation, its per pass conversion is not less than 50%, and 1,3-butadiene does not lose and has increase; A liquid phase part bottom one-stage hydrogenation reactor outlet separating tank is circulated to first stage reactor entrance, and the total conversion rate generating 1,3-butadiene at first stage reactor medium vinyl acetylene selective hydrogenation is greater than 95%.
In the specific implementation, in step (2), the operational condition of rectifying is: working pressure 0.4 ~ 0.6MPa, reflux ratio 18 ~ 23.
By rectifying, obtain in this column overhead the liquid phase material being rich in 1,3-butadiene, wherein the total content of vinylacetylene and ethylacetylene is less than 3%, and 1,3-butadiene content is greater than 90%; This material is as the raw material of butadiene extraction unit.
In the specific implementation, in step (3), the whole selective hydrogenation of alkynes, diolefine is converted into 1-butylene and 2-butylene, and hydrogenation reaction can select hydrogenation catalyst well known in the prior art, such as selective hydrogenation catalyst disclosed in CN200910080849.3.Hydrogenation catalyst is take pseudo-boehmite as carrier; Containing nickel, molybdenum, zinc and silicon in described catalyst for hydrogenation, described nickel, molybdenum, zinc and silicon account for 15 ~ 35%, 1 ~ 2%, 1 ~ 2%, 1.2 ~ 4% of total catalyst weight respectively, and preferably 20 ~ 30%, 1.2 ~ 1.8%, 1.2 ~ 1.6%, 1.5 ~ 3%;
The condition of described hydrogenation reaction is: reactor inlet temperature is 20 ~ 60 DEG C, pressure is 1.2 ~ 2.5MPa, the mol ratio of hydrogen and alkynes, diolefine is 1.1 ~ 3, recycle feed volume ratio is 25 ~ 50, preferred hydrogenation operation condition is: reactor inlet temperature is 30 ~ 50 DEG C, pressure is 1.3 ~ 1.6MPa, and the mol ratio of hydrogen and alkynes, diolefine is 1.2 ~ 1.4, and recycle feed volume ratio is 30 ~ 45.
In secondary hydrogenation reaction, 1,3-divinyl, 1,2-divinyl, vinylacetylene, ethylacetylene selective hydrogenation generate butene-1 and butene-2, transformation efficiency is 100%, in reactor outlet material, alkynes, diene content are less than 10ppm, and this material can as the raw material of butene-1 retrieving arrangement.
The tail gas being rich in alkynes that the present invention discharges with butadiene extraction unit is for raw material, and carrying out selective hydrogenation at first stage reactor, is 1,3-butadiene by the vinylacetylene hydrocracking in tail gas.Hydrogenation products enters butadiene recovery column, obtains the material being rich in 1,3-butadiene by rectifying from tower top, and this material 1,3-butadiene content is high, and vinylacetylene, ethylacetylene content are very low, are suitable as the raw material of butadiene extraction unit.Butadiene recovery column still material is mainly containing 1-butylene, 2-butylene, ethylacetylene, 1,2-divinyl, 1,3-divinyl, second stage reactor is delivered to after the pressurization of this material, alkynes, diolefine selective hydrogenation are converted into 1-butylene, reaction product is rich in 1-butylene, and this material can be used as the raw material of 1-butylene retrieving arrangement to reclaim 1-butylene.The method had both added the output of 1.3-divinyl and 1-butylene, and again reduce load and the energy consumption of butadiene extraction unit, divinyl tail gas is fully used, remarkable in economical benefits.
Accompanying drawing explanation
Fig. 1 is the process flow diagram of divinyl waste gas utilization method of the present invention.
Nomenclature:
The divinyl tail gas of 1 liquefaction; 2 one sections of hydrogen feed; 3 one-stage hydrogenation reactors; 4 one-stage hydrogenation reactor products; 5 one section outlet water coolers; 6 one section outlet separating tanks; 7 non-condensable gases; 8 one sections of recycle pumps; 9 one sections of circulation fluids; 10 one section outlet separating tanks go the liquid phase of butadiene recovery column; 11 butadiene recovery column; 12 condensers; 13 return tanks; 14 non-condensable gases; 15 reflux pumps; 1,3-butadiene material is rich on 16 butadiene recovery column tops; 17 butadiene recovery column still materials; 18 second stage reactor fresh feed pump 19 2 sections hydrogen feed; 20 second-stage hydrogenation reactor chargings; 21 second-stage hydrogenation reactors; 22 second-stage hydrogenation reactor products; 23 second stage exit water coolers; 24 second stage exit separating tanks; 25 non-condensable gases; 26 are rich in 1-butylene material; 27 2 sections of circulation fluids; 28 2 sections of recycle pumps
Embodiment
Be described in further detail technical scheme of the present invention below in conjunction with drawings and Examples, protection scope of the present invention is not limited to following embodiment.
Embodiment 1
From the divinyl tail gas 1 that butadiene extraction unit has liquefied, temperature 30 DEG C, flow 1000kg/h, the 20000kg/h liquid phase 9 come with second stage exit separating tank and 22kg/h hydrogen 2 mix, and enter from the top of first stage reactor 3.The entry condition of first stage reactor is: temperature 40 DEG C, pressure 1.5MPa, the mol ratio of hydrogen and divinyl tail gas 1 medium vinyl acetylene in hydrogen/vinylacetylene mol ratio 1.03:1(hydrogen 2), one section of reaction product 4 enters water cooler 5, with entering one section outlet separating tank 6 after water cooling, a liquid phase part mixes with divinyl tail gas 1 after recycle pump 8 boosts, another liquid phase material 10 enters in the middle part of butadiene recovery column, non-condensable gas 7 discharger of tank top.In butadiene recovery column 11, top gaseous phase enters condenser 12 with delivering to return tank 13 after water cooling, non-condensable gas 14 discharger, phlegma is the C-4-fraction being rich in 1,3-butadiene, and part reflux pump 15 delivers to trim the top of column, another part 16 send butadiene extraction unit to make raw material, this gang of mass flow 748.9kg/h, 1,3-butadiene content is 94.42mol%.Kettle material 17 mixes with the liquid phase 27 of second stage exit separating tank 24 and hydrogen 19 after pressurizeing with pump 18, enters from second stage reactor 21 top.Hydrogen 19 flow is 10.5kg/h, circulation fluid 27 flow 10000kg/h.The entry condition of second stage reactor is: temperature 42 DEG C, pressure 1.5MPa, hydrogen in hydrogen/(alkynes+diolefine) mol ratio 1.14:1(hydrogen 19: alkynes and diolefine sum in butadiene recovery column still 17).Second stage exit material 22 at second stage exit water cooler 23 with being water-cooled to 43 DEG C, enter into second stage exit separating tank 24, non-condensable gas 25 carrying device, liquid phase is the material being rich in 1-butylene, a part 27 to be pressurizeed Posterior circle to two section entrance with pump 28, another part 26 delivers to 1-butylene retrieving arrangement to reclaim 1-butylene, this gang of material 26 flow 234kg/h, 1-butylene content 55.23mol%.
The catalyzer that one-stage hydrogenation uses, using aluminum oxide as carrier, take palladium as active ingredient, with Ag, Mg, K for modified component; Palladium accounts for 3% of described catalyst weight, and modified component Ag, Mg, K account for 1.5%, 2%, 0.05% of described catalyst weight; One-stage hydrogenation reactor inlet temperature is 40 DEG C, and pressure is 1.5MPa, and in one-stage hydrogenation reactor inlet material, the mol ratio of hydrogen and vinylacetylene is 1.03:1, and one section of recycle feed volume ratio is 20; In one-stage hydrogenation reactor, the total conversion rate of vinylacetylene is 96.25%, and in divinyl tail gas (logistics 1), the content of 1,3-butadiene is 40.99%, after reaction, and in first stage reactor outlet streams 4, the content of 1,3-butadiene is increased to 76.9%.
The working pressure of butadiene recovery column is 0.65MPaG, and reflux ratio is 20.Through rectifying separation, from the liquid phase material 16 being rich in 1,3-butadiene that tower top obtains, wherein the content of 1,3-butadiene is 94.42%, and the total content of vinylacetylene and ethylacetylene is low (being 1.29%), and this material is suitable as the raw material of butadiene extraction unit.From the material 17 that tower reactor obtains, the content of 1,3-butadiene, 1，2-butadiene, ethylacetylene, vinylacetylene is higher (being 81.99%), this material be applicable to doing further selec-tive hydrogenation generate butene-1 raw material.The catalyzer that secondary hydrogenation uses is carrier with pseudo-boehmite, and containing nickel, molybdenum, zinc and silicon in catalyzer, nickel accounts for 25% of total catalyst weight, and molybdenum accounts for 1.5% of total catalyst weight, and zinc accounts for 1.4% of total catalyst weight, and silicon accounts for 2% of total catalyst weight.Second-stage hydrogenation reactor temperature in is 42 DEG C, and pressure is 1.5MPa, and the mol ratio of hydrogen and alkynes, diolefine is 1.26:1, and two sections of recycle feed volume ratios are 44.In second-stage hydrogenation reactor, the total conversion rate of alkynes, diolefine is 100%, and the selectivity generating butene-1 is high.In the charging (logistics 17) of second stage reactor, alkynes, diene content are 81.99%, and butene-1 content is 0.16%.After reaction, not containing alkynes, diolefine in second stage reactor outlet streams 26, butene-1 content is increased to 55.23%.This logistics is suitable as the raw material of butene-1 retrieving arrangement.
The quality group prejudice table 1 of each main streams.
Table 1
Continued 1
Claims (6)
1. a method of hydrotreating for divinyl tail gas, the method comprises the following steps successively:
(1) from the divinyl tail gas of butadiene extraction unit, post liquefaction with mix from the liquid phase of one-stage hydrogenation reactor outlet separating tank and a section feeding hydrogen after, enter one-stage hydrogenation reactor top, carry out selective hydrogenation reaction; Reaction product enters one-stage hydrogenation reaction outlet separating tank after cooling, the tank deck non-condensable gas carrying device that described one-stage hydrogenation reaction outlet separating tank obtains, liquid phase at the bottom of the tank obtained, a part is circulated to one-stage hydrogenation reactor inlet, and rest part enters butadiene recovery column;
Described one-stage hydrogenation reactor is heat-insulating fixed-bed reactor; The catalyzer of described selective hydrogenation reaction: to be selected from one or more in aluminum oxide, gac, carbon black, zeolite, molecular sieve and silicon oxide as carrier, take palladium as active ingredient, to be selected from one or more in Bi, Sb, Pb, In, the VIIIth race's element being different from palladium, IB race element, rare earth element, alkali metal, alkali earth metal and halogens for modified component; Described active ingredient accounts for 0.01 ~ 50% of described catalyst weight, and described modified component accounts for 0.1 ~ 20% of described catalyst weight;
The condition of described selective hydrogenation reaction is: reactor inlet temperature is 10 ~ 80 DEG C, and pressure is 1.0 ~ 3.0MPa, and in the mixture entering described hydrogenator, the mol ratio of hydrogen and vinylacetylene is 1 ~ 5, and recycle feed volume ratio is 10 ~ 30; Described recycle feed volume ratio is be circulated to the inventory of one-stage hydrogenation reactor inlet and the ratio of described post liquefaction divinyl tail gas inventory from described one-stage hydrogenation reaction outlet separating tank;
(2) from liquid phase rectifying in described butadiene recovery column of described one-stage hydrogenation reaction outlet separating tank; The top gaseous phase overhead product of described butadiene recovery column is after overcooling, gas-liquid separation, what obtain is main containing 1, the liquid phase material of 3-divinyl send butadiene extraction unit, the non-condensable gas discharger obtained, and the kettle material of described butadiene recovery column enters second-stage hydrogenation reactor after boosting;
The working pressure of described butadiene recovery column is 0.3 ~ 0.8MPa, and reflux ratio is 10 ~ 30;
(3) react after the liquid phase that exports separating tank and two section feeding hydrogen mix from kettle material and the secondary hydrogenation of described butadiene recovery column, enter second-stage hydrogenation reactor top, carry out hydrogenation reaction; Described hydrogenation reaction product enters described second-stage hydrogenation reactor outlet separating tank after being cooled to 30 ~ 50 DEG C, the tank deck non-condensable gas carrying device that described secondary hydrogenation reaction outlet separating tank obtains, liquid phase at the bottom of the tank obtained, a part is circulated to second-stage hydrogenation reactor entrance, and rest part send 1-butylene tripping device to reclaim 1-butylene;
Described second-stage hydrogenation reactor is heat-insulating fixed-bed reactor; The catalyzer of described hydrogenation reaction: take pseudo-boehmite as carrier; Containing nickel, molybdenum, zinc in catalyzer, described nickel account for total catalyst weight 10 ~ 40%, described molybdenum account for total catalyst weight 0.5 ~ 3%, described zinc accounts for 0.5 ~ 3% of total catalyst weight; Described catalyzer is also containing IA race element, and described IA race element accounts for 0.1 ~ 5% of total catalyst weight;
The condition of described hydrogenation reaction is: reactor inlet temperature is 10 ~ 80 DEG C, and pressure is 1.0 ~ 3.0MPa, and enter hydrogen and alkynes in the mixture of described hydrogenator, the mol ratio of diolefine is 1 ~ 5, recycle feed volume ratio is 20 ~ 60; Described recycle feed volume ratio is be circulated to the inventory of second-stage hydrogenation reactor entrance and the ratio entering second stage reactor inventory from butadiene recovery column still from described second-stage hydrogenation reactor outlet separating tank;
Described divinyl tail gas contains: butane 0 ~ 5 % by weight, butylene 0 ~ 15 % by weight, divinyl 20 ~ 60 % by weight, ethylacetylene and vinylacetylene 20 ~ 50 % by weight.
2. method of hydrotreating according to claim 1, is characterized in that:
In step (1), described selective hydrogenation catalyst, using aluminum oxide as carrier, take palladium as active ingredient, with Ag, Mg and K for modified component; Described active component palladium accounts for 0.1 ~ 10% of catalyst weight, and described modified component Ag, Mg, K account for 0.01 ~ 10%, 0.01 ~ 5%, 0.01 ~ 2% of catalyst weight respectively;
The condition of described selective hydrogenation reaction is: reactor inlet temperature is 30 ~ 60 DEG C, and pressure is 1.2 ~ 2.0MPa, and the mol ratio of described hydrogen and vinylacetylene is 1 ~ 1.5, and recycle feed volume ratio is 15 ~ 25.
3. method of hydrotreating according to claim 2, is characterized in that:
Described active component palladium accounts for 2 ~ 4% of described catalyst weight, and described modified component Ag, Mg, K account for 1 ~ 2%, 1 ~ 3%, 0.03 ~ 1% of described catalyst weight respectively;
The condition of described selective hydrogenation reaction is: reactor inlet temperature is 35 ~ 50 DEG C, and pressure is 1.4 ~ 1.6MPa, and the mol ratio of described hydrogen and vinylacetylene is 1 ~ 1.2, and recycle feed volume ratio is 17 ~ 23.
4. method of hydrotreating according to claim 1, is characterized in that:
In step (2), the working pressure of described butadiene recovery column is 0.4 ~ 0.6MPa, and reflux ratio is 18 ~ 23.
5. method of hydrotreating according to claim 1, is characterized in that:
In step (3), containing nickel, molybdenum, zinc and silicon in described catalyst for hydrogenation, described nickel, molybdenum, zinc and silicon account for 15 ~ 35%, 1 ~ 2%, 1 ~ 2%, 1.2 ~ 4% of total catalyst weight respectively;
The condition of described hydrogenation reaction is: reactor inlet temperature is 20 ~ 60 DEG C, and pressure is 1.2 ~ 2.5MPa, and the mol ratio of hydrogen and alkynes, diolefine is 1.1 ~ 3, and recycle feed volume ratio is 25 ~ 50.
6. method of hydrotreating according to claim 5, is characterized in that:
Described nickel, molybdenum, zinc and silicon account for 20 ~ 30%, 1.2 ~ 1.8%, 1.2 ~ 1.6%, 1.5 ~ 3% of total catalyst weight respectively;
The condition of described hydrogenation reaction is: reactor inlet temperature is 30 ~ 50 DEG C, and pressure is 1.3 ~ 1.6MPa, and the mol ratio of hydrogen and alkynes, diolefine is 1.2 ~ 1.4, and recycle feed volume ratio is 30 ~ 45.
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Families Citing this family (10)
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| CN105585411A (en) * | 2014-10-21 | 2016-05-18 | 中国石油化工股份有限公司 | Hydrogenation method of butadiene extraction tail gas |
| CN108779045A (en) * | 2016-03-31 | 2018-11-09 | 日本瑞翁株式会社 | Method for hydrogenation |
| CN109265306A (en) * | 2017-07-17 | 2019-01-25 | 中国石化工程建设有限公司 | A kind of carbon four adds four method of hydrotreating of process units and carbon of hydrogen |
| CN109485536B (en) * | 2017-09-13 | 2021-07-30 | 中国石油化工股份有限公司 | Selective hydrogenation method for alkyne and/or diene in carbon four fraction |
| CN108927173B (en) * | 2018-08-06 | 2021-11-23 | 沈阳沈科姆科技有限公司 | Alkyne selective hydrogenation catalyst and preparation method and application thereof |
| CN114478176B (en) * | 2020-10-26 | 2024-07-02 | 中国石油化工股份有限公司 | Butadiene extraction tail gas selective hydrogenation device and selective hydrogenation method |
| CN114478163A (en) * | 2020-10-26 | 2022-05-13 | 中国石油化工股份有限公司 | Selective hydrogenation device and selective hydrogenation method for butadiene extraction tail gas |
| CN114478164B (en) * | 2020-10-26 | 2023-09-08 | 中国石油化工股份有限公司 | Butadiene extraction tail gas selective hydrogenation device and selective hydrogenation method |
| CN114478162B (en) * | 2020-10-26 | 2023-09-08 | 中国石油化工股份有限公司 | Butadiene extraction tail gas selective hydrogenation device and selective hydrogenation method |
| CN116178093A (en) * | 2022-12-15 | 2023-05-30 | 惠州宇新化工有限责任公司 | Alkyne hydrogenation feeding optimization method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1590353A (en) * | 2003-08-26 | 2005-03-09 | 中国石化集团齐鲁石油化工公司 | Utilization method of butadiene extraction device residue |
| CN1665761A (en) * | 2002-08-08 | 2005-09-07 | 催化蒸馏技术公司 | Selective hydrogenation of acetylenes |
| CN101434508A (en) * | 2008-12-11 | 2009-05-20 | 中国石油天然气股份有限公司 | Selective hydrogenation method for alkyne |
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