CN103013564A - Method for preparing ethylene cracking raw materials by hydrogenating light C5 fractions - Google Patents
Method for preparing ethylene cracking raw materials by hydrogenating light C5 fractions Download PDFInfo
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- CN103013564A CN103013564A CN201110290525XA CN201110290525A CN103013564A CN 103013564 A CN103013564 A CN 103013564A CN 201110290525X A CN201110290525X A CN 201110290525XA CN 201110290525 A CN201110290525 A CN 201110290525A CN 103013564 A CN103013564 A CN 103013564A
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Abstract
The invention provides a method for preparing ethylene cracking raw materials by hydrogenating light C5 fractions. The method comprises the steps that the hydrogenated light C5 fraction raw materials are subjected to hydrogenation reaction via a hydrogenation catalyst fixed bed in the presence of hydrogen to convert unsaturated hydrocarbons in the light C5 fraction raw materials to saturated hydrocarbons, and part of the hydrogenation products returns as solvents and passes through the hydrogenation catalyst fixed bed together with the raw materials after being mixed with the raw materials, wherein the feeding weight ratio of the latter to the former is 1:(6-10); and the hydrogenation products as the solvents are desulfurized by a desulfurizer fixed bed before being mixed with the raw materials, wherein the desulfurizer is active component loaded modified granular activated carbon, the active components are CuO and ZnO, the content of the active components in the desulfurizer is 2-5wt%, and the atomic number ratio of Cu to Zn is 1:(0.2-0.6). The method has the advantages that the light C5 fraction materials with content of active sulfides being about 0.002wt% can be hydrogenated; and the desulfurizer and the hydrogenation catalyst can guarantee long-period operation.
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 and contain active sulfide through the method for hydrogenation reaction for the preparation of the raw material of cracking ethylene preparation.
Background technology
The traditional raw material of industrial preparing ethylene by steam cracking is petroleum naphtha, and along with day by day shortage of petroleum resources, the lighter hydrocarbons resource take C4～C6 as main component that the oil refining process produces is also more come the more to be used.With respect to petroleum naphtha, lighter hydrocarbons are because component is lighter, therefore can obtain higher ethene and propene yield.But, contain higher unsaturated hydrocarbons in this light hydrocarbon materials, the alkynes that mainly comprises alkene, diolefine and small amount, under the hot environment of pyrolyzer, thereby the reactions such as polymerization, cyclisation or condensation will occur unsaturated hydrocarbons causes producing a large amount of cokings, so these light hydrocarbon materials must just can be used as first the raw material of preparing ethylene by steam cracking after hydrogenation reaction makes unsaturated hydrocarbons be converted into stable hydrocarbon.Such as " the C4 hydrogenation of olefins is produced the technical study of feed ethylene " (" petrochemical technology and application ", the 5th phase of the 22nd volume, in September, 2004) literary composition has been introduced the C4 fraction that how catalytic cracking unit is produced prepared ethylene cracking material behind hydrogenation, and article also systematically carried out the investigation of technique and catalyst stability.
The a considerable amount of C 5 fractions of the byproduct in process of naphtha steam cracking ethene processed, the comprehensive utilization of carbon current 5 distillate most worthy are to produce m-pentadiene, isoprene and three kinds of diolefins of dicyclopentadiene that wherein economic worth is higher by separation of extractive distillation.Before the C 5 fraction separation of extractive distillation diolefin, must first a part be contained carbon five feed separation of carbon four lighter hydrocarbons out, this part material accounts for about the 20wt% of C 5 fraction total amount, industrially usually this material is called the lightweight C 5 fraction.The lightweight C 5 fraction also is a kind of lighter hydrocarbons that can be used as preparing ethylene by steam cracking, wherein contains equally higher unsaturated hydrocarbons, also must be through hydrogenation reaction to remove unsaturated hydrocarbons before the cracking.
The desirable catalyzer of hydrogenation reaction of unsaturated hydrocarbon is the loaded catalyst take palladium metal or metallic nickel as active ingredient, and is classical such as Pd/Al
2O
3Catalyzer, Ni/ diatomite catalyzer etc.But day by day serious along with petroleum resources in poor quality trend, oil refining adopts the proportion of high sulfur content crude oil obviously to increase, in the light hydrocarbon materials that above-mentioned oil refining process produces enrichment a considerable amount of active sulfides, such as thiomethyl alcohol, sulfur alcohol, dithiocarbonic anhydride and dimethyl sulfide etc., 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 ‰, Pd/Al
2O
3, Ni/ diatomite one class hydrogenation catalyst just is easy to poison and loses activity.
" the C4 hydrogenation of olefins is produced the technical study of feed ethylene " literary composition has been introduced and has been adopted the catalyzer of sulfide type more easily to be 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 of diolefin, as described herein, in the C4 fraction, contain seldom 1 of amount, during the 3-divinyl, whole hydrogenation process must divide two sections to carry out, and first diolefine is converted into the hydrogenation that carries out again monoolefine behind the monoolefine.The first paragraph 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.
There has been the desulfurization technology of multiple maturation in prior art, processes as adopting gac as sweetening agent the material of sulfur compound to be carried out desulfurization.The active group that active carbon desulfurization mainly relies on activated carbon surface is realized the katalysis of sulfide and oxygen reaction, be converted into elemental sulfur by charcoal absorption after the sulfide reaction, so gac is had catalysis and adsorption concurrently in sweetening process.Common gac is for H
2S one class inorganic sulfur has higher removal efficiency, and to organosulfur, particularly the effect that removes of lower boiling organosulfur is relatively relatively poor.Prior art generally makes load iron in the gac, copper, nickel, cobalt, chromium or the metallic compounds such as basic metal, alkaline-earth metal carry out modification to gac by pickling process, to improve it to the catalytic adsorption performance of organosulfur.Such as " The Influence of the Addition of Cobalt, Nickel, Manganese and Vanadium to Active Carbon on Their Efficiently in SO
2Removal from Stack Gases. " [" Fuel " 1992,71 (11)] literary composition introduced Co
2+, V
5+, Ni
2+And Mn
4+Introduce behind the gac of result of study to(for) the active carbon desulfurization improved performance Deng metal ion, " research of modified activated carbon sorbent desulfurization performance " (" application chemical industry " 05 phase in 2010) one literary composition prompting load its desulphurizing activated being significantly improved of modified activated carbon of a certain amount of CuO.
Yet, usually the suitable desulfurization treatment temp of modified activated carbon is about 50 ℃, and as previously mentioned, contain in the lightweight C 5 fraction 1 of autohemagglutination just very easily occurs under the relatively large room temperature, diolefin and the alkynes such as 3-divinyl, isoprene, cyclopentadiene and 2-butyne, the oligopolymer that polymerization produces can gather at modified activated carbon, covers the catalytic active site of modified active carbon surface and the micropore of obstruction gac, and modified activated carbon will be lost catalysis and the adsorption function to sulfide very soon.
Summary of the invention
The invention provides a kind of method of lightweight C 5 fraction Hydrogenation ethylene cracking material, hydrogenation reaction adopts active higher Ni/ diatomite catalyzer, the present invention cooperates conventional active carbon desulfurization technology, designed a kind of new hydrogenation technique flow process, technical problem to be solved is still can carry out smoothly hydrogenation when active sulfide content is higher in the raw material, and hydrogenation catalyst can keep hydrogenation activity for a long time.
Below be the concrete technical scheme of the present invention:
A kind of method of lightweight C 5 fraction Hydrogenation ethylene cracking material, the method comprises by the lightweight C 5 fraction raw material of hydrogenation in the presence of hydrogen, carries out hydrogenation reaction so that the unsaturated hydrocarbons in the lightweight C 5 fraction raw material is converted into stable hydrocarbon by the hydrogenation catalyst fixed bed.The product of hydrogenation reaction partly return as solvent with mixed by the lightweight C 5 fraction raw material of hydrogenation after common by the hydrogenation catalyst fixed bed, be 1 by the lightweight C 5 fraction raw material of hydrogenation with the weight ratio that feeds intake as the hydrogenation reaction product of solvent: (6～10).
What the present invention was different from prior art is, as the hydrogenation products of solvent with mixed by the lightweight C 5 fraction raw material of hydrogenation before carry out desulfurization by the sweetening agent fixed bed first.The processing condition of desulfurization are: the volume liquid hourly space velocity is 3.0～16.0hr
-1System pressure is 0.2～0.6MPaG, feeding temperature is 5～60 ℃, sweetening agent the has been load modified particles shaped activated carbon of active ingredient, its particle diameter is 3～6mm, active ingredient is CuO and ZnO, and the content of active ingredient is 2～5wt% in the sweetening agent, and the atomicity ratio of Cu and Zn is 1: (0.2～0.6).
Volume liquid hourly space velocity in the above-mentioned sulfur removal technology condition is preferably 4.0～12.0hr
-1System pressure is preferably 0.3～0.5MPaG; Feeding temperature is preferably 10～40 ℃; The granular active carbon of sweetening agent is preferably selected the ature of coal granular active carbon.
Above-mentioned hydrogenation reaction can adopt conventional processing condition, and be generally: the volume liquid hourly space velocity is 4.0～20.0hr
-1, system pressure is 1.0～4.0MPaG, feeding temperature is controlled to be 20～100 ℃, by the lightweight C 5 fraction raw material of hydrogenation in the total amount of unsaturated hydrocarbons wherein, hydrogen be (2～5) by the molar ratio of the lightweight C 5 fraction raw material of hydrogenation: 1.The hydrogenation catalyst of recommendation of the present invention is take Ni as active constituent and the loaded catalyst take diatomite as carrier, and the content of Ni is 30～50wt% in the catalyzer.
In the processing condition of above-mentioned hydrogenation reaction, the volume liquid hourly space velocity is preferably 6.0～12.0hr
-1System pressure is preferably 1.5～3.0MPa; Feeding temperature is preferably 30～60 ℃; Hydrogen be preferably (3～4) by the molar ratio of the lightweight C 5 fraction raw material of hydrogenation: 1; Be preferably 1 by the lightweight C 5 fraction raw material of hydrogenation and the weight ratio that feeds intake as the hydrogenation reaction product of solvent: (7～9).
In technical scheme provided by the invention, the Ni/ diatomite catalyzer of employing is classical hydrogenation of unsaturated hydrocarbons catalyzer, and this is a kind of take Ni as active constituent and the loaded catalyst take diatomite as carrier.Catalyzer can adopt conventional pickling process to be prepared, and first diatomite is configured as particle and makes carrier, then with the solution impregnation that contains Ni salt Ni is loaded on the carrier, and drying, high-temperature roasting, reduction are processed and sieved and make the catalyzer finished product again.
Conventional method is also adopted in the preparation of sweetening agent; as adopting commercially available ature of coal granulated active carbon as carrier; be mixed with steeping fluid with water miscible Cu salt and Zu salt (such as cupric nitrate, zinc nitrate); load on the gac by the salt of equi-volume impregnating with Cu, Zu, again drying, roasting and sieve and make the sweetening agent finished product.
Because hydrogenation process is thermopositive reaction, usually need to be by being removed reaction heat with the temperature of control beds to adding solvent in the raw material of hydrogenation.To adopt the alkane of C4～C6 all be suitable in the present invention in theory, and directly adopt hydrogenation products as obviously the most economical rationality of solvent, and this also is industrial operational means commonly used.The present invention has utilized this point just, and its key problem in technology is to have changed before hydrogenation raw material is carried out the traditional habit that desulfurization is processed, and desulfurization is processed carried out for this part hydrogenation products that returns as solvent after being placed on hydrogenation reaction.Owing to substantially not containing unsaturated hydrocarbons in the hydrogenation products, this catalytic active site with regard to the modified active carbon surface having avoided occuring because of gathering of oligopolymer in sweetening process duct capped and gac is blocked, and sweetening agent can keep higher sulfur removal rate for a long time.
On the other hand, through hydrogenation products that desulfurization is processed as solvent with mixed by required processing requirement by the raw material of hydrogenation after, enter that active sulfide content significantly reduces in the material of hydrogenation catalyst fixed bed.The active sulfide that contains in the lightweight C 5 fraction Hydrogenation ethylene cracking material generally speaking is 0.02wt about ‰, according to the required solvent adding amount of routine, enter in the material of hydrogenation catalyst fixed bed active sulfide content and can guarantee to be reduced to 0.003wt below ‰, this has just guaranteed that hydrogenation catalyst can long period ground steady running.
Compared with prior art advantage of the present invention is very remarkable, can be that the lightweight C 5 fraction material of 0.02wt about ‰ carries out hydrogenation to active sulfide content, and sweetening agent and hydrogenation catalyst all can guarantee long-term operation.500 hours back end hydrogenation beds hydrogenation activities of operation still can remain unchanged substantially continuously, and sweetening agent has also still kept higher sulfur removal rate, and can reach more than 8000 hours the actual service life of hydrogenation catalyst and sweetening agent.
Lightweight C 5 fraction material wherein carbon four unsaturated hydrocarbons behind hydrogenation are converted into butane, and chain carbon five and straight chain carbon five unsaturated hydrocarbons are separately converted to iso-pentane and Skellysolve A.Result of practical application shows, hydrogenation products is used for producing ethene with steam cracking process, and yield of ethene reaches about 35%, and propene yield reaches about 18%.
The invention will be further described below by specific embodiment, and in an embodiment, the definition of the saturation exponent of volume liquid hourly space velocity, unsaturated hydrocarbons is respectively:
Annotate: hydrogenation material is to comprise as the hydrogenation products of solvent with by the mixture of the lightweight C 5 fraction raw material of hydrogenation.
Embodiment
The lightweight C 5 fraction feed composition that embodiment adopts sees the following form:
[embodiment 1～10]
Hydrogenation reaction is carried out in stainless steel tubular type reactor, and reactor is that one ruler cun is the stainless steel tubular type reactor of φ 25mm * 1000mm.Filling 100mL hydrogenation catalyst consists of fixed bed in the reaction tubes, and hydrogenation catalyst is take Ni as active constituent and the loaded catalyst take diatomite as carrier, and the weight percentage of Ni is 30～50% in the catalyzer, reactor bottom filling inert ceramic balls.Need before the charging with hydrogen live catalyst to be activated.
It is to carry out in the stainless steel tubular type reactor of φ 25mm * 1000mm that the desulfurization of hydrogenation products is processed very little at one ruler.Filling 200mL sweetening agent consists of fixed bed in reactor.Sweetening agent the has been load modified particles shaped activated carbon of active ingredient, its particle diameter is 3～6mm, and active ingredient is CuO and ZnO, and the content of active ingredient is 2～5wt% in the sweetening agent, and the atomicity ratio of Cu and Zn is 1: (0.2～0.6).Sweetening agent carried out first processed before operation, available 250 ℃ high temperature nitrogen purges bed, and nitrogen flow is set as 1000NmL/min, and purge time is 12 hours, was down to room temperature after processing finishes for subsequent use.The hydrogenation products that previous experiment prepares is sent into reactor with pump and is carried out the desulfurization processing from the bottom.
Lightweight C 5 fraction raw material mixes in required ratio with the hydrogenation products of processing through desulfurization, after preheating, send into hydrogenator with the speed of setting by the top with pump, hydrogen enters in the reactor by gas distributor, enters the hydrogenation catalyst bed layer after the mixture of lightweight C 5 fraction raw material and the hydrogenation products of processing through desulfurization and hydrogen mix and carries out hydrogenation reaction.Hydrogenation products enters a gas-liquid separator by the hydrogenator bottom, and liquid phase material enters product storage tank.Emptying after entering the wet gas meter metering after the variable valve decompression by the unreacting hydrogen that gas-liquid separator is told, or Returning reacting system after the compression.
A part of hydrogenation products in the product storage tank is sent into desulphurization reactor, sends into the material allocation system of hydrogenation reaction after desulfurization is processed as solvent, and whole device so begins the normal running operation.
The hydrogenation reaction that each embodiment is concrete and desulfurization treatment process condition see Table respectively 1 and table 2.
Table 1.
* carbon five is lightweight C 5 fraction raw material, and in the total amount of unsaturated hydrocarbons wherein;
* carbon five is lightweight C 5 fraction raw material;
* * solvent is hydrogenation products.
Table 2.
Get respectively the hydrogenation products that hydrogenation reaction has been carried out 72 hours and 500 hours, carry out compositional analysis and calculate saturation exponent with vapor-phase chromatography.And get respectively the material that hydrogenator has been carried out 72 hours and entered in 500 hours to hydrogenation reaction, namely as the hydrogenation products of solvent and by the mixture of the lightweight C 5 fraction raw material of hydrogenation, measure active sulfide content with chromatogram-atomic emission spectrum method.The results are shown in Table 3.
Table 3.
Claims (11)
1. the method for a lightweight C 5 fraction Hydrogenation ethylene cracking material, the method comprises by the lightweight C 5 fraction raw material of hydrogenation carries out hydrogenation reaction so that the unsaturated hydrocarbons in the lightweight C 5 fraction raw material is converted into stable hydrocarbon by the hydrogenation catalyst fixed bed in the presence of hydrogen, the product of hydrogenation reaction partly return as solvent with mixed by the lightweight C 5 fraction raw material of hydrogenation after common by the hydrogenation catalyst fixed bed, be 1 by the lightweight C 5 fraction raw material of hydrogenation with the weight ratio that feeds intake as the hydrogenation reaction product of solvent: (6～10) is characterized in that:
As the hydrogenation products of solvent with mixed by the lightweight C 5 fraction raw material of hydrogenation before carry out desulfurization by the sweetening agent fixed bed first, the processing condition of desulfurization are: the volume liquid hourly space velocity is 3.0～16.0hr
-1System pressure is 0.2～0.6MPaG, feeding temperature is 5～60 ℃, sweetening agent the has been load modified particles shaped activated carbon of active ingredient, its particle diameter is 3～6mm, active ingredient is CuO and ZnO, and the content of active ingredient is 2～5wt% in the sweetening agent, and the atomicity ratio of Cu and Zn is 1: (0.2～0.6).
2. the method for lightweight C 5 fraction Hydrogenation ethylene cracking material according to claim 1 is characterized in that the volume liquid hourly space velocity in the described sulfur removal technology condition is 4.0～12.0hr
-1
3. the method for lightweight C 5 fraction Hydrogenation ethylene cracking material according to claim 1 is characterized in that the system pressure in the described sulfur removal technology condition is 0.3～0.5MPaG.
4. the method for lightweight C 5 fraction Hydrogenation ethylene cracking material according to claim 1 is characterized in that the feeding temperature in the described sulfur removal technology condition is 10～40 ℃.
5. the method for lightweight C 5 fraction Hydrogenation ethylene cracking material according to claim 1 is characterized in that described granular active carbon is the ature of coal granular active carbon.
6. the method for lightweight C 5 fraction Hydrogenation ethylene cracking material according to claim 1, it is characterized in that the processing condition of described hydrogenation reaction are: the volume liquid hourly space velocity is 4.0～20.0hr
-1System pressure is 1.0～4.0MPaG, feeding temperature is 20～100 ℃, by the lightweight C 5 fraction raw material of hydrogenation in the total amount of unsaturated hydrocarbons wherein, hydrogen be (2～5) by the molar ratio of the lightweight C 5 fraction raw material of hydrogenation: 1, hydrogenation catalyst is take Ni as active constituent and the loaded catalyst take diatomite as carrier, and the content of Ni is 30～50wt% in the catalyzer.
7. the method for lightweight C 5 fraction Hydrogenation ethylene cracking material according to claim 6 is characterized in that described volume liquid hourly space velocity is 6.0～12.0hr
-1
8. the method for lightweight C 5 fraction Hydrogenation ethylene cracking material according to claim 6 is characterized in that described system pressure is 1.5～3.0MPa.
9. the method for lightweight C 5 fraction Hydrogenation ethylene cracking material according to claim 6 is characterized in that described feeding temperature is 30～60 ℃.
10. the method for lightweight C 5 fraction Hydrogenation ethylene cracking material according to claim 6 is characterized in that described hydrogen and is (3～4) by the molar ratio of the lightweight C 5 fraction raw material of hydrogenation: 1.
11. according to claim 1 or the method for 6 described lightweight C 5 fraction Hydrogenation ethylene cracking materials, it is characterized in that described is 1 by the lightweight C 5 fraction raw material of hydrogenation with the weight ratio that feeds intake as the hydrogenation reaction product of solvent: (7～9).
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Citations (5)
| 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 |
| CN1135456A (en) * | 1996-01-11 | 1996-11-13 | 湖北省化学研究所 | Active-carbon finely sweetening agent and preparation thereof |
| JP2001089772A (en) * | 1999-07-21 | 2001-04-03 | Kobe Steel Ltd | Method for hydrogenolysis of petroleium-based heavy oil |
| 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 |
| CN1765489A (en) * | 2004-10-29 | 2006-05-03 | 中国石油化工股份有限公司 | Supported type active carbon and its preparation method |
-
2011
- 2011-09-28 CN CN201110290525.XA patent/CN103013564B/en not_active Expired - Fee Related
Patent Citations (5)
| 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 |
| CN1135456A (en) * | 1996-01-11 | 1996-11-13 | 湖北省化学研究所 | Active-carbon finely sweetening agent and preparation thereof |
| JP2001089772A (en) * | 1999-07-21 | 2001-04-03 | Kobe Steel Ltd | Method for hydrogenolysis of petroleium-based heavy oil |
| 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 |
| CN1765489A (en) * | 2004-10-29 | 2006-05-03 | 中国石油化工股份有限公司 | Supported type active carbon and its preparation method |
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