CN102041035A - Reformate deolefination method without hydrogen - Google Patents
Reformate deolefination method without hydrogen Download PDFInfo
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Abstract
The invention relates to a reformate deolefination method without hydrogen, which is mainly used for solving the problems in the prior art that deolefination refining agent is low in activity, short in service life and great in aromatic hydrocarbon loss. The technical scheme adopted by the invention is as follows: olefins in reformate are removed because of polymerization or alkylation reaction carried out on a catalyst for 0.3-20h<-1> at the temperature of 120-240 DEG C and under the pressure of 0.5-3.0 MPa, wherein the catalyst contains 0.1-10 parts by weight of at least one metal or oxide thereof selected from Ni, MO, Zr, and Nb, 0.01-2.00 parts by weight of at least one element or oxide thereof selected from Cl, Br and S, 0.05-5 parts by weight of at least one element or oxide thereof selected from F and P, 20-90 parts by weight of molecular sieve and 10-80 parts by weight of at least one selected from SiO2 and Al2O3 or a mixture thereof, thus the problems in the prior art are solved. The method can be used for industrial production of olefin reduction in reformate.
Description
Technical field
The present invention relates to the efficient deolefination method of reformate under a kind of conditions of non-hydrogen.
Background technology
The isomerization unit adsorption separation process is sorbent used very responsive to alkene in the Aromatic Hydrocarbon United Plant; even the content of olefin impurity has only ppm; also can produce very adverse influence to technological process; in order to protect sorbent material; generally before benzenol hydrorefining, be provided with refining step, to remove trace amounts of olefin contained in each burst charging.The reformate olefin(e) centent is the highest in the charging of each burst of benzenol hydrorefining, is the purified emphasis.
Most enterprises all adopt clay-filtered technology to remove trace amounts of olefin in the reformate 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 reformate, polymerization, generate higher-boiling compound, adsorbed by carclazyte then, perhaps in the later separation flow process, remove.
Remove alkene in the reformate with clay-filtered route, to removing alkene in the wide fraction from benzene to dimethylbenzene effect is preferably arranged, but because the carclazyte activity is low, life-span is short, need frequent the replacing, thereby cause the usage quantity of carclazyte very big, the labour intensity height has seriously restricted device " long surely excellent " operation.In recent years, along with the popularization of low pressure heavy adjusting technique, olefin(e) centent further raises in the reformate, and the problems referred to above are aggravation further.
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.
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.
People such as Chen Zhiming have 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.
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.
Adopting olefinic hydrocarbon expelling catalyzer to substitute industrial carclazyte is a new research field, and achievement in research in this respect is few at present, and obtained technological achievement is limited, and the catalyst activity of exploitation is low, the life-span short, and the aromatic hydrocarbons loss is big, does not also possess industrial application value.
Summary of the invention
Technical problem to be solved by this invention is that prior art adopts industrial carclazyte as the deolefination finishing agent, exists activity low, and the life-span is short, and the problem that the aromatic hydrocarbons loss is big provides a kind of new reformate non-hydrogen deolefination method.This method has the active height of deolefination, and the aromatic hydrocarbons loss is little, the advantage that the life-span is long.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of reformate non-hydrogen deolefination method, reaction process does not have hydrogen to participate in, reaction raw materials is the Aromatic Hydrocarbon United Plant reformate, in temperature of reaction is 120～240 ℃, reaction pressure is 0.5～3.0MPa, and reaction velocity 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 comprises following component in parts by weight:
A) in element, 0.1～10 part of at least a metal or its oxide compound that is selected from Ni, Mo, Zr or Nb;
B) in element, 0.01～2.00 part of at least a element or its oxide compound that is selected among Cl, Br, the S;
C) in element, 0.05～5 part of at least a element or its oxide compound that is selected from F, P;
D) 20～90 parts molecular sieve;
E) 10～80 parts are selected from SiO
2Or Al
2O
3In at least a.
In the technique scheme, containing at least two kinds of elements that are selected from silicon, aluminium, titanium in the framework of molecular sieve, can be a kind of molecular sieve, also can be the mixture of two or more molecular sieves, is 40～90 parts in parts by weight molecular sieve consumption preferable range; The element of at least a Ni of being selected from, Mo, Zr or Nb or its oxide compound are 0.3～8.0 part in element consumption preferable range; Element or its oxide compound are 0.05～1.5 part in element consumption preferable range among at least a Cl of being selected from, Br or the S; At least a F of being selected from, P element or its oxide compound are 0.30～5.0 part in element consumption preferable range; Be selected from SiO
2Or Al
2O
3In at least a consumption preferable range be 10～60 parts; In this catalyzer a)+b)+c) the total consumption preferable range of component be less than 10.5 parts.
Preparation of catalysts method of the present invention is as follows: with the molecular sieve and the SiO of aequum
2Or Al
2O
3Powder mixes, and in the process of mechanical mixing, will contain Ni, Mo, Zr, Nb, P, S, F, the Cl of aequum, salt or its compound solution of Br element adds 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 the solid super-strong acid principle that molecular sieve is modified, make it have higher acid amount, simultaneously strength of acid is carried out modulation, make catalyzer obtain suitable strength of acid and acid distribution, thereby provide a large amount of active centre, 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 molecular sieve that the present invention program adopts to the adsorptive power of colloid and reaction product a little less than, effectively slowed down the speed that active sites is capped, the pore passage structure of molecular sieve homogeneous has also suppressed degree of depth polyreaction, has further prolonged catalyst life.
The catalyzer that the present invention relates to is used for the reaction of reformate deolefination, and 170 ℃ of temperature of reaction, pressure 2.0MPa is during mass space velocity 3.0
-1Condition under, its result is: initial activity can reach 98.25%, the life-span surpasses 3000 hours, under the situation of needs, catalyzer of the present invention can be realized regeneration, has obtained better technical effect.
The present invention is further elaborated below by embodiment.
Embodiment
[embodiment 1]
Get Na
2O content is pseudo-boehmite 10 grams of 0.15% (weight), with K
2O content is that MCM-41 molecular sieve 90 grams of 0.30% (weight) mix.With chemical pure nickelous nitrate 4.95 grams, 10% hydrochloric acid, 0.10 gram, 85% phosphatase 11,3.02 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 A-1 that consists of Ni/Cl/P/ molecular sieve/aluminum oxide=1.0/0.01/3.5/90/10 in 550 ℃ of roastings 3 hours.
[embodiment 2]
Get SiO
2Content is silicon sol 50 grams of 40% (weight), with K
2O content is that MCM-41 molecular sieve 80 grams of 0.30% (weight) mix.With chemical pure ammonium molybdate 0.18 gram, 10% brometo de amonio, 0.73 gram, 85% phosphatase 79 .30 gram, chemical pure Neutral ammonium fluoride 4.87 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 catalyst A-2 that consists of Mo/Br/F/P/ molecular sieve/aluminum oxide=0.1/0.05/2.5/2.5/90/10 in 550 ℃ of roastings 3 hours.
[embodiment 3]
Get Na
2O content is pseudo-boehmite 80 grams of 0.15% (weight), with K
2O content is that TS-1 molecular sieve 20 grams of 0.30% (weight) mix.With chemical pure niobic acid 17.23 grams, chemical pure nickelous nitrate 4.95 grams, 98% sulfuric acid, 0.94 gram, 85% phosphoric acid, 0.19 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 A-3 that consists of Nb/Ni/S/P/ molecular sieve/aluminum oxide=9.0/1.0/0.3/0.05/20/80 in 550 ℃ of roastings 3 hours.
[embodiment 4]
Get Na
2O content is pseudo-boehmite 50 grams of 0.15% (weight), with Na
2O content is that mordenite 50 grams of 0.30% (weight) mix.With chemical pure nickelous nitrate 7.43 grams, 98% sulfuric acid, 3.75 grams, 85% phosphatase 11 .12 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 consists of Ni/S/P/ molecular sieve/aluminum oxide=1.5/1.2/0.3/50/50 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 ZSM-5 molecular sieve 20 grams of 0.30% (weight) mix.With chemical pure zirconium nitrate 7.44 grams, 98% sulfuric acid, 6.25 grams, chemical pure Neutral ammonium fluoride 0.97 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 consists of Zr/S/F/ molecular sieve/aluminum oxide=2.0/2.0/0.5/40/60 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 X zeolite 50 grams of 0.30% (weight) mix.With chemical pure niobic acid 13.40 grams, chemical pure zirconium nitrate 3.72 grams, 10% hydrochloric acid, 3.08 grams, 98% sulfuric acid, 1.56 grams, chemical pure Neutral ammonium fluoride 0.10 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 catalyzer D that consists of Nb/Zr/Cl/S/F/ molecular sieve/aluminum oxide=7.0/1.0/0.3/0.5/30/70 in 550 ℃ of roastings 3 hours.
[embodiment 7]
Get Na
2O content is pseudo-boehmite 50 grams of 0.15% (weight), with Na
2O content is that ZSM-5 molecular sieve 50 grams of 0.30% (weight) mix.With chemical pure ammonium molybdate 0.18 gram, chemical pure nickelous nitrate 0.99 gram, 98% sulfuric acid, 4.69 grams, 85% phosphoric acid, 7.44 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-1 that consists of Mo/Ni/S/P/ molecular sieve/aluminum oxide=0.1/0.2/1.5/2.0/50/50 in 550 ℃ of roastings 3 hours.
[embodiment 8]
Get Na
2O content is pseudo-boehmite 50 grams of 0.15% (weight), with Na
2O content is that ZSM-5 molecular sieve 50 grams of 0.30% (weight) mix.With chemical pure ammonium molybdate 0.55 gram, 10% brometo de amonio, 2.90 grams, 98% sulfuric acid, 1.56 grams, 85% phosphatase 11 .86 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 E-2 that consists of Mo/Br/S/P/ molecular sieve/aluminum oxide=0.3/0.2/0.5/0.5/50/50 in 550 ℃ of roastings 3 hours.
[embodiment 9]
Get Na
2O content is pseudo-boehmite 50 grams of 0.15% (weight), with Na
2O content is that Y zeolite 50 grams of 0.30% (weight) mix.With chemical pure nickelous nitrate 4.95 grams, chemical pure zirconium nitrate 3.72 grams, 98% sulfuric acid, 2.50 grams, 85% phosphoric acid, 2.98 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 F that consists of Ni/Zr/S/P/ molecular sieve/aluminum oxide=1.0/1.0/0.8/0.8/50/50 in 550 ℃ of roastings 3 hours.
[embodiment 10]
Get Na
2O content is pseudo-boehmite 60 grams of 0.15% (weight), with Na
2O content is that MCM-41 molecular sieve 40 grams of 0.30% (weight) mix.With chemical pure niobic acid 9.57 grams, 10% brometo de amonio, 4.35 grams, chemical pure Neutral ammonium fluoride 6.82 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 G that consists of Nb/Br/F/ molecular sieve/aluminum oxide=5.0/0.3/3.5/40/60 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 0.73 gram, 98% sulfuric acid, 0.31 gram, 85% phosphatase 11 .12 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 consists of W/S/P/ molecular sieve/aluminum oxide=0.5/0.1/0.3//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 that beta-molecular sieve 70 grams of 0.30% (weight) mix.With chemical pure zirconium nitrate 5.58 grams, 98% sulfuric acid, 0.47 gram, chemical pure antimonous oxide 0.36 gram, 85% phosphatase 11 .86 gram, 2.5 milliliters in chemical pure nitric acid and 20 ml water wiring solution-formings.This mixing solutions is added in this mixture, mix, mediate extruded moulding, dry the back, make the catalyst I-1 that consists of Zr/S/Sb/P/ molecular sieve/aluminum oxide=1.5/0.15/0.3/0.5/50/50 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 of 0.30% (weight) mix.With chemical pure niobic acid 9.57 grams, chemical pure ammonium molybdate 0.28 gram, 98% sulfuric acid, 0.31 gram, chemical pure boric acid 1.72 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-2 that consists of Nb/Mo/S/B/ molecular sieve/aluminum oxide=5.0/0.15/0.1/0.3/50/50 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 P.
[embodiment 14]
Carried out the test of reformate non-hydrogen deolefination with catalyzer that makes among the embodiment 1～13 and Comparative Examples P 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 15]
With catalyzer D described in the embodiment 6, 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 | 98.25 | 0.25 |
| 100 hours | 97.86 | 0.21 |
| 200 hours | 97.52 | 0.21 |
| 300 hours | 97.36 | 0.20 |
| 500 hours | 96.84 | 0.23 |
| 1000 hours | 95.78 | 0.23 |
| 1500 hours | 94.44 | 0.17 |
| 2000 hours | 93.29 | 0.15 |
| 3000 hours | 90.27 | 0.19 |
[embodiment 16]
To the catalyzer D of examination described in the embodiment 15 after 3000 hours, carried out roasting regeneration, on fixed-bed reactor, carried out the stability test of reformate deolefination then, 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 3.
Table 3 regenerated catalyst stability test result
| Runtime, the time | Activity, % | The aromatic hydrocarbons loss |
| 2 hours | 98.41 | 0.30 |
| 100 hours | 97.90 | 0.27 |
| 200 hours | 97.35 | 0.22 |
| 300 hours | 97.04 | 0.21 |
| 500 hours | 96.76 | 0.25 |
| 1000 hours | 95.55 | 0.19 |
| 1500 hours | 93.89 | 0.22 |
| 2000 hours | 93.25 | 0.18 |
| 3000 hours | 90.03 | 0.20 |
By table 3 as seen, this new catalyst regeneration back performance is recovered substantially fully, illustrates that it has good regenerability, thereby prolongs its industrial work-ing life greatly.
[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 J 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) B 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 catalyzer K that consists of molecular sieve/kaolin/aluminum oxide=35/15/50 in 550 ℃ of roastings 3 hours.
[comparative example 4]
With catalyzer J and K described in the Comparative Examples 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 J is lower, and its initial activity has only 85.36%, and the initial activity of catalyzer K is 93.64%, but decay is very fast, and aromatic hydrocarbons loss simultaneously is higher.
[embodiment 17]
With catalyzer D described in the embodiment 6, 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, h |
| 120 | 86.91 | / | 53 |
| 135 | 88.08 | 0.05 | 59 |
| 150 | 88.76 | 0.12 | 77 |
| 170 | 89.11 | 0.16 | 85 |
| 185 | 90.26 | 0.25 | 89 |
| 200 | 91.51 | 0.36 | 76 |
| 220 | 93.22 | 0.44 | 55 |
| 240 | 95.43 | 0.51 | 40 |
[embodiment 18]
With catalyzer G described in the embodiment 10, 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, h |
| 0.5 | 88.90 | 0.16 | 76 |
| 1.0 | 88.94 | 0.17 | 76 |
| 1.5 | 88.89 | 0.14 | 77 |
| 2.0 | 88.76 | 0.12 | 76 |
| 3.0 | 88.90 | 0.17 | 77 |
| 0.3 | 88.76 | 0.14 | 64 |
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 19]
With catalyzer G described in the embodiment 10, 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, h -1 | Initial activity, % | The aromatic hydrocarbons loss, % | Life-span, h |
| 0.3 | 99.54 | 0.48 | 2738 |
| 3.0 | 98.41 | 0.30 | 2149 |
| 10.0 | 92.09 | 0.25 | 381 |
| 20.0 | 89.11 | 0.16 | 106 |
Claims (8)
1. reformate non-hydrogen deolefination method, reaction process do not have hydrogen to participate in, and reaction raw materials is the Aromatic Hydrocarbon United Plant reformate, is 120～240 ℃ in temperature of reaction, and reaction pressure is 0.5～3.0MPa, and reaction velocity 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 comprises following component in parts by weight:
A) in element, 0.1～10 part of at least a metal or its oxide compound that is selected from Ni, Mo, Zr or Nb;
B) in element, 0.01～2.00 part of at least a element or its oxide compound that is selected among Cl, Br, the S;
C) in element, 0.05～5 part of at least a element or its oxide compound that is selected from F, P;
D) 20～90 parts molecular sieve;
E) 10～80 parts are selected from SiO
2Or Al
2O
3In at least a.
2. according to the described reformate non-hydrogen of claim 1 deolefination method, it is characterized in that counting 0.3～8.0 part with element in the consumption of at least a Ni of being selected from of parts by weight, Mo, Zr or Nb element or its oxide compound.
3. according to the described reformate non-hydrogen of claim 1 deolefination method, 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, is 40～90 parts in parts by weight molecular sieve consumption.
4. according to the described reformate non-hydrogen of claim 1 deolefination method, it is characterized in that the molecular sieve that contains in this catalyzer can be a kind of molecular sieve, also can be the mixture of two or more molecular sieves.
5. according to the described reformate non-hydrogen of claim 1 deolefination method, it is characterized in that counting 0.05～1.5 part with element in the consumption of element or its oxide compound among at least a Cl of being selected from of parts by weight, Br, the S.
6. according to the described reformate non-hydrogen of claim 1 deolefination method, it is characterized in that the consumption that is selected from least a or its oxide compound in F, the P element in parts by weight counts 0.30～5.0 part with element.
7. according to the described reformate non-hydrogen of claim 1 deolefination method, it is characterized in that in this catalyzer of parts by weight a)+b)+c) the total consumption of component less than 10.5 parts.
8. according to the described reformate non-hydrogen of claim 1 deolefination method, it is characterized in that being selected from SiO in parts by weight
2Or Al
2O
3In at least a consumption be 10～60 parts.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009102016361A CN102041035B (en) | 2009-10-13 | 2009-10-13 | Reformate deolefination method without hydrogen |
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| Application Number | Priority Date | Filing Date | Title |
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| CN2009102016361A CN102041035B (en) | 2009-10-13 | 2009-10-13 | Reformate deolefination method without hydrogen |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014044195A1 (en) * | 2012-09-21 | 2014-03-27 | 中国石油化工股份有限公司 | Reformate hydrotreatment method |
| WO2017197515A1 (en) * | 2016-05-16 | 2017-11-23 | Meg Energy Corp. | Direct olefin reduction of thermally cracked hydrocarbon streams |
| US9862896B2 (en) | 2012-09-21 | 2018-01-09 | China Petroleum & Chemical Corporation | Hydrocarbon oil hydrotreating method |
| CN107754845A (en) * | 2016-08-23 | 2018-03-06 | 中国石油化工股份有限公司 | High life reformate olefine lowering catalyst |
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2009
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014044195A1 (en) * | 2012-09-21 | 2014-03-27 | 中国石油化工股份有限公司 | Reformate hydrotreatment method |
| US9862896B2 (en) | 2012-09-21 | 2018-01-09 | China Petroleum & Chemical Corporation | Hydrocarbon oil hydrotreating method |
| US9879186B2 (en) | 2012-09-21 | 2018-01-30 | China Petroleum & Chemical Corporation | Reformate hydrotreatment method |
| WO2017197515A1 (en) * | 2016-05-16 | 2017-11-23 | Meg Energy Corp. | Direct olefin reduction of thermally cracked hydrocarbon streams |
| CN109153923A (en) * | 2016-05-16 | 2019-01-04 | Meg能源公司 | The direct Olefin decrease of thermal cracking hydrocarbon stream |
| CN107754845A (en) * | 2016-08-23 | 2018-03-06 | 中国石油化工股份有限公司 | High life reformate olefine lowering catalyst |
| CN107754845B (en) * | 2016-08-23 | 2020-03-27 | 中国石油化工股份有限公司 | Long-life catalyst for reducing olefins in reformate |
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| CN102041035B (en) | 2013-01-09 |
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