CN102776021A - Preparation method for raw material used for cracking production of ethylene through hydrogenation of lightweight C5 fraction - Google Patents
Preparation method for raw material used for cracking production of ethylene through hydrogenation of lightweight C5 fraction Download PDFInfo
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- CN102776021A CN102776021A CN2011101192611A CN201110119261A CN102776021A CN 102776021 A CN102776021 A CN 102776021A CN 2011101192611 A CN2011101192611 A CN 2011101192611A CN 201110119261 A CN201110119261 A CN 201110119261A CN 102776021 A CN102776021 A CN 102776021A
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Abstract
The invention provides a preparation method for a raw material used for cracking production of ethylene through hydrogenation of a lightweight C5 fraction. The method comprises a step of mixing the lightweight C5 fraction with a solvent and a step of subjecting the mixture to a hydrogenation reaction in the presence of mixed gas of CO and H2 under the action of a catalyst bed layer of a fixed bed, wherein volume liquid hourly space velocity is 1.0 to 5.0 hr<-1>, system pressure is 1.0 to 4.0 MPa, feeding temperature of reactants is 20 to 100 DEG C, the volume percentage content of CO in the mixed gas of CO and H2 is 0.0005 to 0.0020%, a used catalyst is a supported catalyst with Ni as an active component and diatomite as a supporter, the weight percentage content of Ni in the catalyst is 10 to 50%, and the solvent is a resultant of the hydrogenation reaction. According to the invention, pure hydrogen commonly used in conventional methods for hydrogenation is replaced by hydrogen containing CO; on the premise that other hydrogenation conditions do not change, hydrogenation of a lightweight C5 fraction material containing 0.0003 to 0.001 wt% of active sulfide can be carried out, hydrogenation activity of the catalyst can be maintained for a long time, and the actual service life of the catalyst can reach more than 8000 h.
Description
Technical field
The present invention relates to a kind of method of hydrotreating that contains the C 5 fraction of unsaturated hydrocarbons, particularly with the C 5 fraction that contains unsaturated hydrocarbons at metal Ni be active ingredient catalyzer in the presence of, be used for the method for the raw material of cracking ethylene preparation through hydrogenation reaction preparation.
Background technology
The traditional raw material of preparing ethylene by steam cracking is a petroleum naphtha in the industry, and along with petroleum resources shortage day by day, what oil refinery process produced is that the lighter hydrocarbons resource of staple also comes the more to be used more with C4～C6.With respect to petroleum naphtha, lighter hydrocarbons are because component is lighter, so can obtain higher ethene and propene yield.But; Contain higher unsaturated hydrocarbons in this light hydrocarbon materials; Mainly comprise alkene, diolefine and more a spot of alkynes; Under the hot environment of pyrolyzer, cause producing a large amount of cokings thereby reactions such as polymerization, cyclisation or condensation will take place unsaturated hydrocarbons, so these light hydrocarbon materials must, hydrogenation reaction just can be used as earlier the raw material of preparing ethylene by steam cracking after making unsaturated hydrocarbons be converted into stable hydrocarbon.Like " the C4 hydrogenation of olefins is produced the technical study of feed ethylene " (" petrochemical technology and application "; The 22nd the 5th phase of volume; In September, 2004) literary composition has been introduced the C 4 fraction that how CCU is produced and behind hydrogenation, has been prepared the cracking of ethylene raw material, and article also systematically carried out the investigation of technology and catalyst stability.
The a considerable amount of C 5 fractions of by-product in the process of naphtha steam cracking system ethene, the comprehensive utilization of carbon current 5 distillate most worthy are to separate through extracting rectifying to produce wherein higher m-pentadiene, isoprene and three kinds of diolefins of NSC 7352 of economic worth.Before the C 5 fraction extracting rectifying separating diolefin, must elder generation be come out by carbon five feed separation that a part contains carbon four lighter hydrocarbons, this part material accounts for about the 30wt% of C 5 fraction total amount, usually this material is called the lightweight C 5 fraction in the industry.The lightweight C 5 fraction also is a kind of lighter hydrocarbons that can be used as preparing ethylene by steam cracking, wherein contains higher unsaturated hydrocarbons equally, also must be through hydrogenation reaction to remove unsaturated hydrocarbons before the cracking.
In the prior art, hydrogenation reaction of unsaturated hydrocarbon ideal catalyzer is for being the loaded catalyst of active ingredient with palladium metal or metallic nickel, and is classical like Pd/Al
2O
3Catalyzer, Ni/ zeyssatite catalyzer etc.But day by day serious along with petroleum resources poor qualityization trend; The oil refinery adopts the proportion of high sulfur content crude oil obviously to increase; In the light hydrocarbon materials that above-mentioned oil refinery process produces enrichment a considerable amount of active sulfides; And palladium metal or metallic nickel are very responsive to active sulfide, when the content of active sulfide in the hydrogenation material surpasses 0.003wt ‰, and Pd/Al
2O
3, one type of hydrogenation catalyst of Ni/ zeyssatite just is easy to poison and loses activity.Therefore the preceding material of hydrogenation has to carry out earlier the desulfurization processing usually, because the active sulphur complicated component, the sweetening process cost is very high, and is difficult to reach the target that purifies, and the content that is about to active sulfide in the material is reduced to 0.003wt below ‰.
" the C4 hydrogenation of olefins is produced the technical study of feed ethylene " literary composition has been introduced the catalyzer that adopts sulfide type and has been prone to poisoned and the problem of inactivation by active sulfide to tackle common metal active constituent; But this catalyzer is obviously not ideal enough for the hydrogenation performance of diolefin; As indicated, when containing the 1,3-butadiene of very small amount in the C 4 fraction; Whole hydrogenation process must divide two sections to carry out, and earlier diolefine is converted into the hydrogenation that carries out alkene behind the monoolefine again.First section hydrogenation reaction is for fear of the autohemagglutination of diolefin, and hydrogenation process must be controlled under the very low reaction conditions of intensity carries out.And the content of diolefin and alkynes is usually up to about 35wt% in the lightweight C 5 fraction, and the catalyzer of this sulfide type obviously is not suitable for the hydrogenation of lightweight C 5 fraction.
Summary of the invention
The invention provides a kind of method of raw material of lightweight C 5 fraction hydrogenation preparing cracking ethylene preparation; Hydrogenation reaction adopts active higher Ni/ zeyssatite catalyzer; Technical problem to be solved by this invention is when active sulfide content is higher in the hydrogenation reaction material, and catalyzer still can keep hydrogenation activity for a long time.
Below be the concrete technical scheme of the present invention:
A kind of method of raw material of lightweight C 5 fraction hydrogenation preparing cracking ethylene preparation; This method comprises with in the presence of CO and hydrogen gas mixture, carrying out hydrogenation reaction through the fixed bed catalyst bed after lightweight C 5 fraction material and the solvent, so that the unsaturated hydrocarbons in the lightweight C 5 fraction material is converted into stable hydrocarbon.The volume liquid hourly space velocity is controlled to be 1.0～5.0hr-1, and system pressure is controlled to be 1.0～4.0MPa, and the reaction-ure feeding temperature is controlled to be 20～100 ℃.Lightweight C 5 fraction material is in the total amount of unsaturated hydrocarbons wherein, and the molar ratio of hydrogen and lightweight C 5 fraction material is (2～5): 1.The volumn concentration of CO is 0.005～0.020 ‰ in CO and the hydrogen gas mixture.Catalyzer is to be active constituent with Ni and to be the loaded catalyst of carrier with zeyssatite, and the weight percentage of Ni is 10～50% in the catalyzer.Solvent adopts the product of this hydrogenation reaction, and the weight ratio that feeds intake of lightweight C 5 fraction material and solvent is 1: (6～10).
Above-mentioned volume liquid hourly space velocity preferably is controlled to be 1.5～3.0hr-1; System pressure preferably is controlled to be 1.5～3.0MPa; The reaction-ure feeding temperature preferably is controlled to be 30～60 ℃.
The molar ratio of above-mentioned hydrogen and lightweight C 5 fraction material is preferably (3～4): 1 (lightweight C 5 fraction material is in the total amount of unsaturated hydrocarbons wherein; The volumn concentration of CO is preferably 0.007～0.010 ‰ in CO and the hydrogen gas mixture.
The weight ratio that feeds intake of above-mentioned lightweight C 5 fraction material and solvent is preferably 1: (7～9).
The Ni/ zeyssatite catalyzer that the present invention adopts is classical hydrogenation of unsaturated hydrocarbons catalyzer; There are two kinds of hydrogenation activity positions in this catalyzer; But the hydrogenation of high reactivity position catalysis monoolefine wherein, but the hydrogenation of the hydrogenation of middle low activity position catalysis diolefin or alkynes and part monoolefine.Behind catalyzer adsorption activity sulfide, after hydrogenation activity has been lost in the high reactivity position,, can't reach as monoolefine content in the lighter hydrocarbons of cracking of ethylene raw material use less than the requirement of 5wt% though middle low activity position has hydrogenation activity.
The absorption of active sulfide on the catalyst activity position is the major cause that influences the catalyst hydrogenation performance; Usually absorption can be divided into two kinds of physical adsorption and chemisorption; Physical adsorption is that sulfide is attached to the hydrogenation activity that the catalyst activity position reduces catalyzer with Van der Waals force; And chemisorption is the strong interaction between sulfide and the catalyst activity position, and the former can cause the reversibility of catalyzer, temporary inactivation, and the latter is irreversible permanent inactivation.
Essence of the present invention is in the atmosphere of hydrogenation, to sneak into proper C O gas.The contriver is through discovering, CO is stronger than active sulfide in Ni/ zeyssatite catalyst surface adsorptive power, and when CO content in the reaction atmosphere reduced, the CO of absorption then can break away from from catalyst surface.In hydrogenation reaction is carried out; When the content of CO in the hydrogen is higher; CO can with the cluster generation complexing action of the hydrogenation activity position of Ni; Combination with co-ordination bond is adsorbed in catalyst surface, and when catalyst surface was adsorbed with active sulfide, CO can remove active sulfide with the metathetical mode from catalyst surface.CO also makes poisoning of catalyst in essence and causes its active reduction after being adsorbed in catalyst surface; But this fortunately inactivation is reversible; As long as CO content in the hydrogen is reduced, catalyst activity is recovered, so just improved the stability of catalyst hydrogenation activity greatly.
The employing of solvent is in order to control hydrogenation reaction heat; The alkane of C4～C6 all is suitable in theory; And directly adopt hydrogenation products as obviously economical rationality the most of solvent; As long as the part of hydrogenation products is returned the raw material mixing system, will have to adopt the C4～C6 alkane of outsourcing when device moves first usually certainly.
Advantage compared with prior art of the present invention very significantly; Whole hydrogenation technique is very simple; Just when hydrogenation, use pure hydrogen instead contain CO hydrogen, under the constant prerequisite of other hydroconversion condition, can adopt the very good Ni/ zeyssatite catalyzer of hydrogenation activity is that the lightweight C 5 fraction material of 0.003～0.01wt ‰ carries out hydrogenation to active sulfide content; Not only exempted the process that removes active sulfide before the hydrogenation; And can improve the stability of catalyst hydrogenation activity greatly, when beds continuously 500 hours back end hydrogenation activity of operation still can remain unchanged basically, can reach more than 8000 hours the actual service life of catalyzer.
Lightweight C 5 fraction material wherein carbon four unsaturated hydrocarbons behind hydrogenation are converted into butane, and chain carbon five is separately converted to iso-pentane and Skellysolve A with straight chain carbon five unsaturated hydrocarbons.Result of practical application shows that hydrogenation products is used for producing ethene with steam cracking process, and yield of ethene reaches about 35%, and propene yield reaches about 18%.
Through concrete embodiment the present invention is done further description below, in an embodiment, the definition of the saturation exponent of volume of liquid air speed, unsaturated hydrocarbons is respectively:
Embodiment
The lightweight C5 fraction feed composition that embodiment adopts sees the following form:
[embodiment 1～10]
Hydrogenation reaction is carried out in stainless steel tubular type reactor drum, and reactor drum is that one ruler cun is the stainless steel tubular type reactor drum of φ 25mm * 1000mm.Filling 100ml catalyzer in the reaction tubes, catalyzer are to be active constituent with Ni and to be the loaded catalyst of carrier with zeyssatite, and the weight percentage of Ni is 30～50% in the catalyzer, reactor bottom filling inert ceramic balls.Need before the charging live catalyst to be carried out activation with hydrogen.
Lightweight C 5 fraction material mixes with the hydrogenation products of previous Experiment Preparation; After preheating, send into hydrogenator with the speed of setting by the top with pump; The mixed gas of hydrogen and CO gets in the reactor drum through gas distributor, and lightweight C 5 fraction material mixes back entering beds and carries out hydrogenation reaction with the mixed gas of hydrogen and CO.Hydrogenation products gets into a gas-liquid separator by the hydrogenator bottom, and liquid phase material gets into product storage tank.The unreacting hydrogen of being told by gas-liquid separator gets into wet gas meter metering back emptying after the variable valve decompression, or compression back Returning reacting system.
The concrete hydrogenation conditions of each embodiment is seen table 1.
[comparative example 1～3]
Do not add CO gas in the hydrogen, be pure hydrogen, all the other are with embodiment 1～10.The concrete hydrogenation conditions of each comparative example is seen table 1.
Get hydrogenation reaction respectively and carried out 72 hours and 500 hours the embodiment and the hydrogenation products of comparative example, carry out compositional analysis and calculate saturation exponent with vapor-phase chromatography, the result sees table 2.
Table 1.
* carbon five is lightweight C5 fraction material, and in the total amount of unsaturated hydrocarbons in the material;
* carbon five is lightweight C5 fraction material;
* * solvent is a hydrogenation products;
The content of CO in ※ hydrogen and the CO mixed gas.
Table 2.
Claims (7)
1. the method for the raw material of a lightweight C 5 fraction hydrogenation preparing cracking ethylene preparation; This method comprises in the presence of CO and hydrogen gas mixture, carrying out hydrogenation reaction through the fixed bed catalyst bed after lightweight C 5 fraction material and the solvent; So that the unsaturated hydrocarbons in the lightweight C 5 fraction material is converted into stable hydrocarbon, the volume liquid hourly space velocity is controlled to be 1.0～5.0hr-1, and system pressure is controlled to be 1.0～4.0MPa; The reaction-ure feeding temperature is controlled to be 20～100 ℃; Lightweight C 5 fraction material is in the total amount of unsaturated hydrocarbons wherein, and the molar ratio of hydrogen and lightweight C 5 fraction material is (2～5): 1, and the volumn concentration of CO is 0.005～0.020 ‰ in CO and the hydrogen gas mixture; Catalyzer is to be active constituent with Ni and to be the loaded catalyst of carrier with zeyssatite; The weight percentage of Ni is 10～50% in the catalyzer, and solvent adopts this hydrogenation reaction product, and the weight ratio that feeds intake of lightweight C 5 fraction material and solvent is 1: (6～10).
2. the method for the raw material of lightweight C 5 fraction hydrogenation preparing cracking ethylene preparation according to claim 1 is characterized in that described volume liquid hourly space velocity is controlled to be 1.5～3.0hr
-1
3. the method for the raw material of lightweight C 5 fraction hydrogenation preparing cracking ethylene preparation according to claim 1 is characterized in that described system pressure is controlled to be 1.5～3.0MPa.
4. the method for the raw material of lightweight C 5 fraction hydrogenation preparing cracking ethylene preparation according to claim 1 is characterized in that described reaction-ure feeding temperature is controlled to be 30～60 ℃.
5. the method for the raw material of lightweight C 5 fraction hydrogenation preparing cracking ethylene preparation according to claim 1; The molar ratio that it is characterized in that described hydrogen and lightweight C 5 fraction material is (3～4): 1, and lightweight C 5 fraction material is in the total amount of unsaturated hydrocarbons wherein.
6. the method for the raw material of lightweight C 5 fraction hydrogenation preparing cracking ethylene preparation according to claim 1, the volumn concentration that it is characterized in that CO in described CO and the hydrogen gas mixture are 0.007～0.010 ‰.
7. the method for the raw material of lightweight C 5 fraction hydrogenation preparing cracking ethylene preparation according to claim 1 is characterized in that the weight ratio that feeds intake of described lightweight C 5 fraction material and solvent is 1: (7～9).
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111099950A (en) * | 2018-10-25 | 2020-05-05 | 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 |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4064152A (en) * | 1975-06-16 | 1977-12-20 | Union Oil Company Of California | Thermally stable nickel-alumina catalysts useful for methanation |
| CN1699309A (en) * | 2004-05-20 | 2005-11-23 | 中国石化上海石油化工股份有限公司 | Process for preparing pentane from light C5 distillate |
-
2011
- 2011-05-10 CN CN2011101192611A patent/CN102776021A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4064152A (en) * | 1975-06-16 | 1977-12-20 | Union Oil Company Of California | Thermally stable nickel-alumina catalysts useful for methanation |
| CN1699309A (en) * | 2004-05-20 | 2005-11-23 | 中国石化上海石油化工股份有限公司 | Process for preparing pentane from light C5 distillate |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111099950A (en) * | 2018-10-25 | 2020-05-05 | 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 |
| 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 |
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Application publication date: 20121114 |