CN102220158A - Method for reducing olefins in aromatic hydrocarbons - Google Patents
Method for reducing olefins in aromatic hydrocarbons Download PDFInfo
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- CN102220158A CN102220158A CN2010101472340A CN201010147234A CN102220158A CN 102220158 A CN102220158 A CN 102220158A CN 2010101472340 A CN2010101472340 A CN 2010101472340A CN 201010147234 A CN201010147234 A CN 201010147234A CN 102220158 A CN102220158 A CN 102220158A
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Abstract
The invention relates to a method for reducing olefins in aromatic hydrocarbons, which mainly solves the problem that carclazyte with low activity is used in a large amount and pollutes the environment and the problem that the regeneration process is complicated and may cause secondary environmental pollution for the active ingredients of the newly developed olefin-removing fine preparation are susceptible to loss and need to be supplemented in the regeneration process in the prior art. The invention better solves the problems by adopting a technical scheme that 0.1 to 5.0 element weight parts of element or oxide of at least one of Ni, Mo, W and Zr, 0.1 to 10.0 element weight parts of element or oxide of at least one of Ti, Cu and Al, 0.01 to 8.0 element weight parts of at least one rare earth element or oxide thereof, 20 to 90 weight parts of molecular sieve and at least one novel catalyst selected from SiO2 and Al2O3 are adopted to perform the polymerization or alkylation of olefins in reformate on the catalyst under the conditions of a temperature between 120 and 240 DEG C, a pressure of 0.5 to 3.0MPa and a speed of .3 to 20h<-1>. The method can be used in industrial production for reducing olefins in the reformate.
Description
Technical field
The present invention relates to a kind of aromatic hydrocarbons and fall olefins process.
Background technology
In Aromatic Hydrocarbon United Plant, in order to obtain qualified Chemicals and to guarantee that subsequent technique carries out smoothly, unit such as reformation, aromatic hydrocarbons extracting, isomerization and toluene disproportionation are equipped with refining step to remove olefin impurity.
Most enterprises all adopt the finishing agent of atlapulgite as refining step on the our times, carclazyte has acid sites, under high-pressure liquid phase, 150～200 ℃ of conditions, have certain catalytic polymerization ability and duct adsorptive power, can make reactions such as the trace amounts of olefin generation hydrocarbonylation that contains in the aromatic hydrocarbons, polymerization, generate higher-boiling compound, adsorbed by carclazyte then, perhaps in the later separation flow process, remove.
Carclazyte is as finishing agent, to removing alkene in the wide fraction from benzene to dimethylbenzene effect is preferably arranged, but it is too short that shortcoming is the life-span, the replacement cycle of many enterprises reformation carclazyte has only 15 days, the consumption of carclazyte is very big, and the labour intensity of changing carclazyte is also very big, has seriously restricted device " long surely excellent " operation, unit scale maximize day by day and the low pressure heavy situation that benefit is promoted all day under, this problem is more and more outstanding.
The exploitation carclazyte can cause the permanent damage of environment.In addition, contain the aromatic hydrocarbons carclazyte because very unfavorable to HUMAN HEALTH behind the inactivation, can't recycle, can only handle by landfill, this has just caused serious secondary pollution to environment.In today that environmental consciousness is constantly strengthened, this problem more and more receives the country and the common people's concern, and manufacturing enterprise presses for the catalysis deolefination technology that can address these problems.
As far back as the eighties in last century, Uop Inc. has just started to develop hydrogenation and has fallen the alkene technology to substitute industrial carclazyte.In recent years, the domestic research work that also begins olefinic hydrocarbon expelling catalyzer.People such as Wang Xin, Chen Zhiming has carried out the research of refining and removing olefin from aromatic hydrocarbon molecular sieve catalyst, the result shows the active NC201 granular carclazyte catalyzer that all uses apparently higher than industry of the deolefination of the HY molecular sieve catalyst that contains different tackiness agents, and it is its well behaved major reason that the molecular sieve catalyst surface has more weak acid center.Carbon distribution is the major cause of molecular sieve catalyst surface inactivation.But this catalyzer performance after using 8 hours is promptly close with industrial carclazyte, illustrates that overall performance is on the low side.
Chinese patent CN1618932 introduced a kind of under conditions of non-hydrogen catalytic refining reformation aromatic hydrocarbon oil catalyzer.This catalyzer adopts kaolin, aluminium stone and beta-molecular sieve to make through extrusion, is the non-loading type solid acid catalyst, adopts this catalyst treatment reformation aromatic hydrocarbon oil, 100～300 ℃ of temperature of reaction, and reaction pressure 0.5～3.0MPa, air speed 0.5～40 o'clock
-1Under the condition, can remove the trace amounts of olefin in the aromatic hydrocarbons.But this catalyst life is still too short, is 548.63mgBr/100g at the raw material bromine index, and air speed is 25 o'clock
-1Examination is after 18 hours under the condition, and its catalyst outlet bromine index just reaches 182mgBr/100g.
Wang Yinan, people such as He Yang remove in the aromatic hydrocarbons trace amounts of olefin to zeolite molecular sieve and study, and adopt the zeolite [molecular sieve of rare-earth elements La modification that the olefin impurity in the aromatic hydrocarbons is carried out deep removal.Experimental result shows that catalyzer adopts mechanical mixing the best; For Z type molecular sieve, it is 10% that the best of rare-earth elements La is added massfraction, and initial activity and life-span all improve a lot.
Shanghai Petroleum Chemical Engineering Institute also takes up to develop the alkene technology of falling that can substitute industrial carclazyte the beginning of this century, and in March, 2009, the aromatic hydrocarbons olefine lowering catalyst has carried out commerical test in Plant of Tianjin Petrochemical Company under the DOT-100 conditions of non-hydrogen of this institute's exploitation.
Adopting olefinic hydrocarbon expelling catalyzer to substitute industrial carclazyte is a new research field, achievement in research in this respect is few at present, the hydrogenation route is because complex process, facility investment is big, the running cost height, the problem that significant loss is big fails to be applied, the olefine lowering catalyst one way life-span under the non-hydrogen route is relatively still shorter, needs device to regenerate outward, because in regenerative process, there is leakage in the contained active ingredient of catalyzer, therefore often need after-teeming, make the reclaiming process complexity, the regeneration cost height, and bring environmental pollution problems, need to be resolved hurrily.
Summary of the invention
Technical problem to be solved by this invention is to fall in the prior art that active ingredient easily runs off in the alkene finishing agent regenerative process, needs after-teeming, thereby makes the reclaiming process complexity, and bring environmental pollution problems, provides a kind of new aromatic hydrocarbons to fall olefins process.This method is used for having when olefine reaction falls in aromatic hydrocarbons the active height of the alkene of falling under the operating mode of industrial carclazyte, the aromatic hydrocarbons loss is few, and the life-span is long, and active ingredient does not run off in the regenerative process, need not the advantage of after-teeming.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is as follows: olefins process falls in a kind of aromatic hydrocarbons, is reaction raw materials with the Aromatic Hydrocarbon United Plant reformate, reaction process does not have hydrogen to participate in, in temperature of reaction is 120～240 ℃, and reaction pressure is 0.5～3.0MPa, and air speed is 0.3～20h
-1Under the condition, reaction raw materials contacts with catalyzer, makes alkene generation alkylation or polyreaction in the raw material, generates macromolecular cpd and removes, and wherein used catalyzer in parts by weight, comprises following component:
A) in element, 0.1～5.0 part of at least a element or oxide compound that is selected from Ni, Mo, W or Zr;
B) in element, 0.1～10.0 part of at least a element or oxide compound that is selected from Ti, Cu or Al;
C) in element, 0.01～8.0 part of at least a rare earth element or oxide compound;
D) 20～90 parts molecular sieve;
E) 10～80 parts of at least a SiO that are selected from
2Or Al
2O
3
In the technique scheme, containing at least two kinds of elements that are selected from silicon, aluminium, titanium or phosphorus in the framework of molecular sieve, can be a kind of molecular sieve, also can be the mixture of two or more molecular sieves.In parts by weight, molecular sieve consumption preferable range is 40～90 parts.In the element wt umber, the element of at least a Ni of being selected from, Mo, W or Zr or oxide compound consumption preferable range are 0.3～3.0 part, the consumption preferable range of the element of at least a Ti of being selected from, Cu or Al or oxide compound is 0.3～8.0 part, the consumption preferable range of at least a rare earth element or oxide compound is 0.05～6.0 part, and more preferably scope is 0.3～4.0 part.In parts by weight, at least a SiO that is selected from
2Or Al
2O
3The consumption preferable range be 10～60 parts.Preferred version is not for needing the after-teeming coagent in the catalyst regeneration process.
The method for preparing catalyst that the present invention adopts is as follows: with the molecular sieve and the SiO of aequum
2Or Al
2O
3Powder mixes, and in the process of mechanical mixing, Ni, Mo, W, Zr, Ti, Cu or Al and the rare earth element solution that will contain aequum add wherein, and machinery is mediated extrusion after 20 minutes, at room temperature dries then.550 degree roastings 3 hours, promptly make the catalyzer finished product after the pelletizing of air dried catalyzer.
The deolefination reaction belongs to the carbonium ion reaction mechanism, the surface acid amount and the strength of acid of catalyzer have material impact to this reaction, wherein the B acid site is the main active centre of reaction, and the L acid site helps out, so the proportionlity of B acid and L acid also has certain influence to reflex action.The strong acid center on finishing agent surface is the active centre of deep reaction, at the strong acid center reaction mass cracking or degree of depth polymerization can take place, thereby causes the aromatic hydrocarbons loss.
The present invention adopts has the molecular sieve of more acid sites as active main body, and adopt auxiliary agent that strength of acid is carried out modulation, obtain suitable strength of acid and acid distribution when making catalyzer obtain higher acid amount, thereby improved activity, suppressed the generation of cracking and degree of depth polyreaction, made catalyzer show advantages of high catalytic activity and stability with respect to industrial carclazyte and other solid acid catalysts.
In addition, the present invention program does not adopt more easily that the evaporable auxiliary agent comes modified catalyst in high-temperature calcination process, and therefore active sites can not run off in regenerative process, has simplified reclaiming process, has reduced regeneration cost, the environmental pollution of having avoided regeneration to bring.
The catalyzer that the present invention relates to is used for aromatic hydrocarbons falls olefine reaction, 170 ℃ of temperature of reaction, pressure 2.0MPa is during mass space velocity 3.0
-1Condition under, its result is: initial activity can reach 97.37%, less than 85% as the inactivation standard, the life-span surpasses 3000 hours with activity, catalyzer of the present invention can repeatedly be regenerated, and need not after-teeming, reclaiming process is simple, has obtained better technical effect.
The present invention is further elaborated below by embodiment, but do not limit the present invention.
Embodiment
[embodiment 1]
Get SiO
2Content is silicon sol 62.5 grams of 40% (weight), with Na
2O content is that SAPO-11 molecular sieve 75 grams of 0.30% (weight) mix.With ammonium molybdate 0.18 gram, chemical pure cupric nitrate 6.98 grams, chemical pure aluminum nitrate 13.9 grams, chemical pure cerous nitrate 0.13 gram, 2.5 milliliters in chemical pure nitric acid and 33 ml water wiring solution-formings.This mixing solutions is added in this mixture, mix, mediate extruded moulding, dry the back, make the catalyst A that parts by weight consist of Mo/Cu/Al/Ce/ molecular sieve/silicon oxide=0.1/1.5/1.0/0.05/75/25 in 550 ℃ of roastings 3 hours.
[embodiment 2]
Get Na
2O content is pseudo-boehmite 80 grams of 0.15% (weight), with Na
2O content is that SAPO-34 molecular sieve 20 grams, chemical pure titanium dioxide 8.34 grams of 0.30% (weight) mix.With chemical pure nickelous nitrate 2.48 grams, chemical pure ammonium tungstate 1.47 grams, chemical pure lanthanum nitrate 0.93 gram, 2.5 milliliters in chemical pure nitric acid and 63 ml water wiring solution-formings.This mixing solutions is added in this mixture, mix, mediate extruded moulding, dry the back, make the catalyst B that parts by weight consist of Ni/W/Ti/La/ molecular sieve/aluminum oxide=0.5/1.0/5.0/0.3/20/80 in 550 ℃ of roastings 3 hours.
[embodiment 3]
Get Na
2O content is pseudo-boehmite 20 grams of 0.15% (weight), with Na
2O content is SAPO-5 molecular sieve 60 grams, the Na of 0.30% (weight)
2O content is that beta-molecular sieve 20 grams, chemical pure titanium dioxide 13.34 grams of 0.30% (weight) mix.With chemical pure nickelous nitrate 3.96 grams, chemical pure lanthanum nitrate 0.03 gram, 2.5 milliliters in chemical pure nitric acid and 63 ml water wiring solution-formings.This mixing solutions is added in this mixture, mix, mediate extruded moulding, dry the back, make the catalyzer C that parts by weight consist of Ni/Ti/La/ molecular sieve/aluminum oxide=0.8/8.0/0.01/80/20 in 550 ℃ of roastings 3 hours.
[embodiment 4]
Get Na
2O content is pseudo-boehmite 10 grams of 0.15% (weight), with Na
2O content is MCM-41 molecular sieve 30 grams, the Na of 0.30% (weight)
2O content is that SAPO-5 molecular sieve 60 grams, chemical pure titanium dioxide 13.34 grams of 0.30% (weight) mix.With ammonium molybdate 2.76 grams, chemical pure nickelous nitrate 7.43 grams, chemical pure lanthanum nitrate 0.3 gram, chemical pure neodymium nitrate 0.46 gram, 2.5 milliliters in chemical pure nitric acid and 63 ml water wiring solution-formings.This mixing solutions is added in this mixture, mix, mediate extruded moulding, dry the back, make the catalyzer D that parts by weight consist of Mo/Ni/Ti/La/Nd/ molecular sieve/aluminum oxide=1.5/1.5/8.0/0.1/0.2/90/10 in 550 ℃ of roastings 3 hours.
[embodiment 5]
Get Na
2O content is pseudo-boehmite 60 grams of 0.15% (weight), with Na
2O content is Y zeolite 20 grams, the Na of 0.30% (weight)
2O content is that SAPO-11 molecular sieve 20 grams, chemical pure cerium dioxide 9.83 grams of 0.30% (weight) mix.With chemical pure zirconium nitrate 9.30 grams, chemical pure cupric nitrate 0.93 gram, chemical pure aluminum nitrate 1.39 grams, 2.5 milliliters in chemical pure nitric acid and 63 ml water wiring solution-formings.This mixing solutions is added in this mixture, mix, mediate extruded moulding, dry the back, make the catalyzer E that parts by weight consist of Zr/Cu/Al/Ce/ molecular sieve/aluminum oxide=2.5/0.2/0.1/8.0/40/60 in 550 ℃ of roastings 3 hours.
[embodiment 6]
Get SiO
2Content is silicon sol 50 grams of 40% (weight), with Na
2O content is pseudo-boehmite 30 grams, the Na of 0.15% (weight)
2O content is that MCM-41 molecular sieve 50 grams, chemical pure zirconium dioxide 3.38 grams, chemical pure titanium dioxide 3.34 grams, chemical pure cerium dioxide 6.14 grams of 0.30% (weight) mix.With chemical pure ammonium tungstate 0.73 gram, chemical pure cupric nitrate 4.65 grams, 2.5 milliliters in chemical pure nitric acid and 33 ml water wiring solution-formings.This mixing solutions is added in this mixture, mix, mediate extruded moulding, dry the back, make the catalyzer F that parts by weight consist of W/Zr/Ti/Cu/Ce/ molecular sieve/silica/alumina=0.5/2.5/2.0/1.0/5.0/50/20/30 in 550 ℃ of roastings 3 hours.
[embodiment 7]
Get Na
2O content is pseudo-boehmite 10 grams of 0.15% (weight), with Na
2O content is that SAPO-5 molecular sieve 90 grams of 0.30% (weight) mix.With chemical pure nickelous nitrate 1.49 grams, chemical pure titanium sulfate 7.52 grams, chemical pure cupric nitrate 6.98 grams, chemical pure cerous nitrate 0.53 gram, 2.5 milliliters in chemical pure nitric acid and 63 ml water wiring solution-formings.This mixing solutions is added in this mixture, mix, mediate extruded moulding, dry the back, make the catalyzer G that parts by weight consist of Ni/Ti/Cu/Ce/ molecular sieve/aluminum oxide=0.3/1.5/1.5/0.2/50/50 in 550 ℃ of roastings 3 hours.
[embodiment 8]
Get Na
2O content is pseudo-boehmite 30 grams of 0.15% (weight), with Na
2O content is that mordenite 70 grams of 0.30% (weight) mix.With chemical pure ammonium molybdate 0.92 gram, chemical pure ammonium tungstate 1.46 grams, chemical pure cupric nitrate 0.47 gram, chemical pure lanthanum nitrate 0.16 gram, chemical pure cerous nitrate 0.27 gram, 2.5 milliliters in chemical pure nitric acid and 63 ml water wiring solution-formings.This mixing solutions is added in this mixture, mix, mediate extruded moulding, dry the back, make the catalyzer H that parts by weight consist of Mo/W/Cu/La/Ce/ molecular sieve/aluminum oxide=0.5/1.0/0.1/0.05/0.1/70/30 in 550 ℃ of roastings 3 hours.
[embodiment 9]
Get Na
2O content is pseudo-boehmite 30 grams of 0.15% (weight), with Na
2O content is mordenite 20 grams, the Na of 0.30% (weight)
2O content is that beta-molecular sieve 50 grams of 0.30% (weight) mix.With chemical pure nickelous nitrate 7.47 grams, chemical pure zirconium nitrate 7.44 grams, chemical pure titanium sulfate 2.51 grams, chemical pure cupric nitrate 1.40 grams, chemical pure aluminum nitrate 4.17 grams, 2.5 milliliters in chemical pure nitric acid and 63 ml water wiring solution-formings.This mixing solutions is added in this mixture, mix, mediate extruded moulding, dry the back, make the catalyst I that parts by weight consist of Ni/Zr/Cu/Ti/Al/ molecular sieve/aluminum oxide=1.5/2.0/0.5/0.3/0.3/0.3/70/30 in 550 ℃ of roastings 3 hours.
[embodiment 10]
Get Na
2O content is pseudo-boehmite 40 grams of 0.15% (weight), with Na
2O content is SAPO-5 molecular sieve 40 grams, the Na of 0.30% (weight)
2O content is that ZSM-5 molecular sieve 20 grams, chemical pure zirconium dioxide 2.70 grams, chemical pure titanium dioxide 16.68 grams of 0.30% (weight) mix.With chemical pure ammonium molybdate 2.76 grams, chemical pure ammonium tungstate 2.20 grams, chemical pure lanthanum nitrate 0.93 gram, 2.5 milliliters in chemical pure nitric acid and 63 ml water wiring solution-formings.This mixing solutions is added in this mixture, mix, mediate extruded moulding, dry the back, make the catalyzer J that parts by weight consist of Mo/W/Zr/Ti/La/ molecular sieve/aluminum oxide=1.5/1.5/2.0/10.0/0.3/60/40 in 550 ℃ of roastings 3 hours.
[embodiment 11]
Get Na
2O content is pseudo-boehmite 50 grams of 0.15% (weight), with Na
2O content is X zeolite 20 grams, the Na of 0.30% (weight)
2O content is that beta-molecular sieve 30 grams of 0.30% (weight) mix.With chemical pure ammonium tungstate 4.40 grams, chemical pure titanium sulfate 0.5 gram, chemical pure cupric nitrate 2.33 grams, chemical pure aluminum nitrate 4.17 grams, chemical pure praseodymium chloride 0.88 gram, chemical pure cerous nitrate 0.80 gram, 2.5 milliliters in chemical pure nitric acid and 63 ml water wiring solution-formings.This mixing solutions is added in this mixture, mix, mediate extruded moulding, dry the back, make the catalyzer K that parts by weight consist of W/Ti/Cu/Al/Pr/Ce/ molecular sieve/aluminum oxide=3.0/0.1/0.5/0.3/0.5/0.3/50/50 in 550 ℃ of roastings 3 hours.
[embodiment 12]
Get SiO
2Content is silicon sol 75 grams of 40% (weight), Na
2O content is ZSM-12 molecular sieve 40 grams, the Na of 0.30% (weight)
2O content is that MCM-41 molecular sieve 30 grams, chemical pure zirconium dioxide 2.70 grams, chemical pure titanium dioxide 13.34 grams of 0.30% (weight) mix.With chemical pure neodymium nitrate 0.92 gram, chemical pure praseodymium chloride 0.53 gram, 2.5 milliliters in chemical pure nitric acid and 30 ml water wiring solution-formings.This mixing solutions is added in this mixture, mix, mediate extruded moulding, dry the back, make the catalyzer L that parts by weight consist of Zr/Ti/Nd/Pr/ molecular sieve/aluminum oxide=2.0/8.0/0.4/0.3/70/30 in 550 ℃ of roastings 3 hours.
[embodiment 13]
Get Na
2O content is pseudo-boehmite 50 grams of 0.15% (weight), Na
2O content is that beta-molecular sieve 50 grams, chemical pure titanium dioxide 16.68 grams of 0.30% (weight) mix.With chemical pure ammonium molybdate 1.84 grams, chemical pure lanthanum nitrate 1.25 grams, 2.5 milliliters in chemical pure nitric acid and 63 ml water wiring solution-formings.This mixing solutions is added in this mixture, mix, mediate extruded moulding, dry the back, make the catalyzer M that parts by weight consist of Mo/Ti/La/ molecular sieve/aluminum oxide=1.0/10.0/0.4/50/50 in 550 ℃ of roastings 3 hours.
[embodiment 14]
Get SiO
2Content is silicon sol 100 grams of 40% (weight), Na
2O content is SAPO-5 molecular sieve 40 grams, the Na of 0.30% (weight)
2O content is that Y zeolite 20 grams of 0.30% (weight) mix.With chemical pure Xiao Suangu 2.47 grams, chemical pure titanium sulfate 7.52 grams, chemical pure cupric nitrate 4.65 grams, chemical pure lanthanum nitrate 0.47 gram, 2.5 milliliters in chemical pure nitric acid and 63 ml water wiring solution-formings.This mixing solutions is added in this mixture, mix, mediate extruded moulding, dry the back, make the catalyst n that parts by weight consist of Co/Ti/Cu/La/ molecular sieve/silicon oxide=0.5/1.5/1.0/0.15/60/40 in 550 ℃ of roastings 3 hours.
[embodiment 15]
Get Na
2O content is pseudo-boehmite 25 grams of 0.15% (weight), Na
2O content is that SAPO-5 molecular sieve 75 grams, chemical pure titanium dioxide 8.34 grams of 0.30% (weight) mix.With chemical pure Xiao Suangu 2.47 grams, chemical pure ammonium tungstate 0.73 gram, chemical pure nitrate of baryta 0.57 gram, 2.5 milliliters in chemical pure nitric acid and 63 ml water wiring solution-formings.This mixing solutions is added in this mixture, mix, mediate extruded moulding, dry the back, make the catalyzer O that parts by weight consist of Co/W/Ti/Ba/ molecular sieve/aluminum oxide=0.5/0.5/5.0/0.3/75/25 in 550 ℃ of roastings 3 hours.
[embodiment 16]
Get Na
2O content is pseudo-boehmite 30 grams of 0.15% (weight), Na
2O content is that ZSM-5 molecular sieve 70 grams of 0.30% (weight) mix.With chemical pure ammonium molybdate 2.21 grams, chemical pure magnesium nitrate 1.06 grams, 2.5 milliliters in chemical pure nitric acid and 63 ml water wiring solution-formings.This mixing solutions is added in this mixture, mix, mediate extruded moulding, dry the back, make the catalyst P that parts by weight consist of Mo/Mg/ molecular sieve/aluminum oxide=1.2/0.1/70/30 in 550 ℃ of roastings 3 hours.
[comparative example 1]
Not doing under the situation that any modification handles, is that the catalyzer of catalyzer and invention carries out performance and contrasts with the atlapulgite, and atlapulgite is numbered Q.
[embodiment 17]
Carried out the test of reformate non-hydrogen deolefination with catalyzer that makes among the embodiment 1～16 and comparative example Q in fixed-bed reactor, raw material is a reformate, and bromine index is 650 milligrams of Br/100 gram oil.Reaction pressure: 2.0MPa, temperature: 160 ℃, air speed: 10.0 o'clock
-1, the results are shown in Table 1 (aromatic hydrocarbons loss refer to react two hours after sampling analysis result).
The reaction result of table 1 different activities pivot catalyzer
[embodiment 18]
With catalyzer E described in the embodiment 5, on fixed-bed reactor, carried out the stability test of reformate deolefination, 170 ℃ of temperature, pressure 2.0MPa, raw material bromine index are 650 milligrams of Br/100 gram oil, during weight space velocity 3.0
-1, the results are shown in Table 2.
Table 2 stability test result
| Runtime, the time | Activity, % | The aromatic hydrocarbons loss |
| 2 hours | 97.37 | 0.24 |
| 100 hours | 96.06 | 0.20 |
| 200 hours | 95.81 | 0.19 |
| 300 hours | 95.73 | 0.18 |
| 500 hours | 95.30 | 0.21 |
| 1000 hours | 94.34 | 0.20 |
| 1500 hours | 93.11 | 0.14 |
| 2000 hours | 92.06 | 0.12 |
| 3000 hours | 89.18 | 0.15 |
[embodiment 19]
To the catalyzer E of examination described in the embodiment 18 after 3000 hours, carried out roasting regeneration, the mode that roasting adopts ascending order to heat up, in roasting process only to system's bubbling air and nitrogen, on fixed-bed reactor, carried out the stability test of reformate deolefination, 170 ℃ of temperature, pressure 2.0MPa with the catalyzer after the regeneration then, the raw material bromine index is 650 milligrams of Br/100 gram oil, during weight space velocity 3.0
-1, the results are shown in Table 3.
Table 3 regenerated catalyst stability test result
| Runtime, the time | Activity, % | The aromatic hydrocarbons loss |
| 2 hours | 96.52 | 0.29 |
| 100 hours | 96.10 | 0.26 |
| 200 hours | 95.64 | 0.21 |
| 300 hours | 95.42 | 0.20 |
| 500 hours | 95.22 | 0.24 |
| 1000 hours | 94.12 | 0.18 |
| 1500 hours | 92.57 | 0.21 |
| 2000 hours | 92.03 | 0.17 |
| 3000 hours | 88.95 | 0.19 |
By table 3 as seen, do not carrying out under the situation of after-teeming active ingredient, this new catalyst regeneration back performance is recovered substantially fully, illustrate that catalyzer of the present invention can regenerate under simple working condition, thereby both simplified operation, having avoided environmental pollution again, is a kind of environmentally friendly catalyzer, and prospects for commercial application is good.
[comparative example 2]
Adopt that Chinese patent CN1618932 introduces a kind of under conditions of non-hydrogen catalytic refining reformation aromatic hydrocarbon oil method for preparing catalyst, get Na
2O content is pseudo-boehmite 50 grams of 0.15% (weight), with Na
2O content be 0.15% (weight) beta-molecular sieve 15 gram, beat kaolin 35 behind the powder and restrain and mix.With 2.5 milliliters in chemical pure nitric acid and 65 ml water wiring solution-formings.This mixing solutions is added in this mixture, mix, mediate extruded moulding, dry the back, make the catalyzer R that consists of molecular sieve/kaolin/aluminum oxide=15/35/50 in 550 ℃ of roastings 3 hours.
[comparative example 3]
Adopt that Chinese patent CN1618932 introduces a kind of under conditions of non-hydrogen catalytic refining reformation aromatic hydrocarbon oil method for preparing catalyst, get Na
2O content is pseudo-boehmite 50 grams of 0.15% (weight), with Na
2O content be 0.15% (weight) beta-molecular sieve 35 gram, beat kaolin 15 behind the powder and restrain and mix.With 2.5 milliliters in chemical pure nitric acid and 65 ml water wiring solution-formings.This mixing solutions is added in this mixture, mix, mediate extruded moulding, dry the back, make the catalyst S that consists of molecular sieve/kaolin/aluminum oxide=35/15/50 in 550 ℃ of roastings 3 hours.
[comparative example 4]
With catalyzer R and S described in the comparative example 2～3, on fixed-bed reactor, carried out the stability test of reformate deolefination, 170 ℃ of temperature, pressure 2.0MPa, raw material bromine index are 650 milligrams of Br/100 gram oil, during weight space velocity 3.0
-1, the results are shown in Table 4.
Table 4 stability test result
By table 4 as seen, the activity of catalyzer R is lower, and its initial activity has only 85.36%, and the initial activity of catalyst S is 93.64%, but decay is very fast, and aromatic hydrocarbons loss simultaneously is higher.
[embodiment 20]
With catalyzer E described in the embodiment 5, on fixed-bed reactor, carried out the test of reformate deolefination temperature condition, pressure 2.0MPa, raw material bromine index are 650 milligrams of Br/100 gram oil, during weight space velocity 20.0
-1, be reduced to 70% as the inactivation standard with activity, the results are shown in Table 5.
Table 5 reformate deolefination temperature condition test-results
| Temperature of reaction, ℃ | Initial activity, % | The aromatic hydrocarbons loss, % | Life-span, hour |
| 120 | 83.47 | 0.05 | 49 |
| 135 | 84.52 | 0.09 | 57 |
| 150 | 86.33 | 0.13 | 75 |
| 170 | 86.65 | 0.17 | 80 |
| 185 | 89.12 | 0.19 | 84 |
| 200 | 89.78 | 0.22 | 75 |
| 220 | 90.26 | 0.34 | 64 |
| 240 | 90.49 | 0.38 | 56 |
As shown in Table 5, temperature of reaction is high more, and its initial activity is high more, but the life-span presents with temperature rising prolongation earlier, the trend that shorten the back.
[embodiment 21]
With catalyzer E described in the embodiment 5, on fixed-bed reactor, carried out the test of reformate deolefination pressure condition, temperature is 150 ℃, the raw material bromine index is 650 milligrams of Br/100 gram oil, during weight space velocity 20.0
-1, be reduced to 70% as the inactivation standard with activity, the results are shown in Table 6.
Table 6 reformate deolefination pressure condition test-results
| Reaction pressure, MPa | Initial activity, % | The aromatic hydrocarbons loss, % | Life-span, hour |
| ?0.5 | 86.33 | 0.13 | 75 |
| ?1.0 | 86.41 | 0.11 | 76 |
| ?1.5 | 86.29 | 0.14 | 73 |
| ?2.0 | 86.32 | 0.15 | 74 |
| ?3.0 | 86.38 | 0.17 | 75 |
| ?0.3 | 86.21 | 0.10 | 67 |
As can be known from Table 6, between 0.5～3.0MPa, reaction pressure does not have obvious influence to catalyst performance, and when pressure was lower than 0.5MPa, catalyst performance decreased.
[embodiment 22]
With catalyzer E described in the embodiment 5, on fixed-bed reactor, carried out reformate deolefination air speed condition test, temperature is 170 ℃, pressure is 2.0MPa, the raw material bromine index is 650 milligrams of Br/100 gram oil, is reduced to 93% as the inactivation standard with activity, the results are shown in Table 7.
Table 7 reformate deolefination weight space velocity condition test result
| Weight space velocity, hour -1 | Initial activity, % | The aromatic hydrocarbons loss, % | Life-span, hour |
| 0.3 | 99.54 | 0.29 | 2876 |
| 3.0 | 97.37 | 0.24 | 1519 |
| 10.0 | 87.29 | 0.31 | 392 * |
| 20.0 | 86.65 | 0.17 | 80 * |
*Be reduced to 70% as the inactivation standard with activity.
Claims (9)
1. olefins process falls in an aromatic hydrocarbons, is reaction raw materials with the Aromatic Hydrocarbon United Plant reformate, and reaction process does not have hydrogen to participate in, and is 120～240 ℃ in temperature of reaction, and reaction pressure is 0.5～3.0MPa, and air speed is 0.3～20h
-1Under the condition, reaction raw materials contacts with catalyzer, makes alkene generation alkylation or polyreaction in the raw material, generates macromolecular cpd and removes, and wherein used catalyzer in parts by weight, comprises following component:
A) in element, 0.1～5.0 part of at least a element or oxide compound that is selected from Ni, Mo, W or Zr;
B) in element, 0.1～10.0 part of at least a element or oxide compound that is selected from Ti, Cu or Al;
C) in element, 0.01～8.0 part of at least a rare earth element or oxide compound;
D) 20～90 parts molecular sieve;
E) 10～80 parts of at least a SiO that are selected from
2Or Al
2O
3
2. fall olefins process according to the described aromatic hydrocarbons of claim 1, it is characterized in that the consumption at least a Ni of being selected from of element wt umber, Mo, W or Zr element or oxide compound is 0.3～3.0 part.
3. fall olefins process according to the described aromatic hydrocarbons of claim 1, it is characterized in that the consumption at least a Ti of being selected from of element wt umber, Cu or Al element or oxide compound is 0.3～8.0 part.
4. fall olefins process according to the described aromatic hydrocarbons of claim 1, it is characterized in that the consumption at least a rare earth element of element wt umber or oxide compound is 0.05～6.0 part.
5. fall olefins process according to the described aromatic hydrocarbons of claim 4, it is characterized in that the consumption at least a rare earth element of element wt umber or oxide compound is 0.3～4.0 part.
6. falling olefins process according to the described aromatic hydrocarbons of claim 1, it is characterized in that containing in the used framework of molecular sieve at least two kinds of elements that are selected from silicon, aluminium, titanium or phosphorus, is 40～90 parts in parts by weight molecular sieve consumption.
7. fall olefins process according to the described aromatic hydrocarbons of claim 1, it is characterized in that the molecular sieve that contains in the catalyzer is the mixture of a kind of molecular sieve or two or more molecular sieves.
8. fall olefins process according to the described aromatic hydrocarbons of claim 1, it is characterized in that at least a SiO of being selected from of parts by weight
2Or Al
2O
3Consumption be 10～60 parts.
9. fall olefins process according to the described aromatic hydrocarbons of claim 1, not needing in the catalyst regeneration process it is characterized in that the after-teeming coagent.
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| CN103805273A (en) * | 2012-11-07 | 2014-05-21 | 中国石油化工股份有限公司 | Method for olefin removal of reformate |
| CN104226359A (en) * | 2013-06-17 | 2014-12-24 | 中国石油化工股份有限公司 | Aromatic alkylation catalyst and synthetic method of mixed xylene |
| CN110813370A (en) * | 2019-10-29 | 2020-02-21 | 浙江工业大学 | Method for refining aromatic hydrocarbon by utilizing microporous mesoporous core-shell structure composite molecular sieve |
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| CN103805273A (en) * | 2012-11-07 | 2014-05-21 | 中国石油化工股份有限公司 | Method for olefin removal of reformate |
| CN104226359A (en) * | 2013-06-17 | 2014-12-24 | 中国石油化工股份有限公司 | Aromatic alkylation catalyst and synthetic method of mixed xylene |
| CN112390699B (en) * | 2019-08-16 | 2023-01-24 | 中国石油化工股份有限公司 | Method for reducing olefin |
| CN112390699A (en) * | 2019-08-16 | 2021-02-23 | 中国石油化工股份有限公司 | Method for reducing olefin |
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| CN112657549B (en) * | 2019-10-15 | 2023-08-08 | 中国石油化工股份有限公司 | Regenerated catalyst and preparation method and application thereof |
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| CN110813370A (en) * | 2019-10-29 | 2020-02-21 | 浙江工业大学 | Method for refining aromatic hydrocarbon by utilizing microporous mesoporous core-shell structure composite molecular sieve |
| CN114870890A (en) * | 2022-03-07 | 2022-08-09 | 宁波中金石化有限公司 | Catalyst for deeply removing olefin in aromatic hydrocarbon and preparation method thereof |
| CN114870890B (en) * | 2022-03-07 | 2024-01-02 | 宁波中金石化有限公司 | Catalyst for deeply removing olefin in aromatic hydrocarbon and preparation method thereof |
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