CN102309977B - Deolefination catalyst and preparation method and application thereof - Google Patents
Deolefination catalyst and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a deolefination catalyst and a preparation method thereof and application of the catalyst to the process of catalyzing and refining reformed oil under the non-hydrogen condition. The catalyst consists of a rare earth modified molecular sieve and zirconium oxide modified inorganic refractory oxide and is used for carrying out catalytic treatment on the reformed oil. Micro olefins in the heavy aromatics can be effectively removed. The content of arenes is slightly increased. The catalyst has high activity and stability.
Description
Technical field
The present invention relates to a kind of olefinic hydrocarbon expelling catalyzer and preparation method thereof, this catalyst is specially adapted in the non-hydrogen refining depth deolefination process of reformed oil.
Background technology
Aromatic hydrocarbons is the important foundation raw material of petrochemical industry, also is widely used at the synthetic aspects such as solvent, explosive, military project and aerospace that reach of fine chemicals.The most important source of aromatic hydrocarbons is a catalytic reforming process at present.Yet easy by-product alkene comprises monoolefine, alkadienes and styrene etc. in the aromatic hydrocarbons production process.These olefin impurities are more active, and their existence meeting exerts an adverse impact to some follow-up chemical engineering processes, such as cause coking etc. in high-temperature reactor.Produce qualified aromatic hydrocarbons and solvent naphtha product, just must take measures this part olefin impurity in the aromatic hydrocarbon product is carried out deep removal.
At present by the refinery the method for olefin impurity that removes in the aromatic hydrocarbons that extensively adopts mainly contain hydrofinishing and clay-filtered two kinds.
Hydrofinishing is to make the saturated generation corresponding paraffins of alkene to reach the method that removes trace amounts of olefin impurity by hydrogenation reaction.Typical catalyst is to be carrier with the aluminium oxide, the load group VIII noble metals, as CN85100760A, CN85100215A, CN1448474A, CN101157031A patent report, hydrofinishing has generally that selectivity is good, catalyst stability is good and advantage such as long service life.But unifining process effect for single benzene narrow fraction is better, and for containing C simultaneously
8A～C
10 +The long distillate product of A, the hydrogenation reaction degree of depth is difficult to take into account comprehensively, can cause aromatic hydrocarbons significantly to lose, and catalyst price height, also needs to consume hydrogen, and production cost is higher.Its deolefination efficient is higher for single aromatic fraction, and for the long distillate that contains multiple aromatic hydrocarbons simultaneously, the degree of depth of hydrogenation reaction is difficult to take into account comprehensively, and causes the loss of aromatic hydrocarbons bigger, and the noble metal price is high, causes the investment cost of refinery to improve.The many large-scale reformer of Jian Liing mainly adopts clay-filtered because cut is wide in recent years.
Clay-filtered is under certain operation condition, thereby can impel alkene in the product liquid superimposed, polymerization or alkylated reaction etc. to take place with the alkene deep removal through the acid activated centre on the acid-treated carclazyte, such as CN101116812A, CN101591212A, but because the deactivation rate of carclazyte is very fast, operation cycle is very short, carclazyte behind the inactivation can not be regenerated again, so its consumption is big, replacing is frequent and carry a large amount of aromatic hydrocarbons, generally can only landfill disposal, serious waste of resources but also cause environmental pollution so not only.
Consider that hydrofinishing and clay-filtered two kinds of methods all have certain shortcoming, therefore the high performance catalyst of the alternative above-mentioned two kinds of technologies of exploitation is very necessary.Because molecular sieve has characteristics such as regular crystal structure and pore passage structure and big acid amount, and performance can adopt the several different methods modulation, is widely used solid acid catalyst.So molecular sieve catalyst can well remedy the deficiency of top two kinds of conventional methods.
CN200410046820.0 disclose a kind of under conditions of non-hydrogen the method for catalytic refining reformation aromatic naphtha, this method catalyst system therefor component is molecular sieve and aluminium oxide, adopt this method catalytic treatment reformation aromatic naphtha, can remove the trace amounts of olefin in the aromatic hydrocarbons effectively, aromatic hydrocarbons does not lose on the contrary to be increased, particularly C
8Aromatic hydrocarbons increases significantly.But still exist the catalyst system therefor activity not high, the high deficiency of product bromine index.
Summary of the invention
For overcoming shortcoming of the prior art, the invention provides olefinic hydrocarbon expelling catalyzer of a kind of activity and good stability and preparation method thereof, and this catalyst application in the catalytic refining reformed oil process under conditions of non-hydrogen, can remove trace amounts of olefin wherein effectively, arene content has increase slightly, and can make device carry out long-term operation.
Olefinic hydrocarbon expelling catalyzer of the present invention is made up of rare earth modified molecular sieve and zirconia modified inorganic refractory oxide, is benchmark with the quality of catalyst, and the content of rare earth modified molecular sieve is 1.0%～99.0%, is preferably 51.0%～80.0%; The content of zirconia modified inorganic refractory oxide is 1.0%～99.0%, is preferably 20.0%～49.0%; In the wherein rare earth modified molecular sieve, the mass content of rare earth oxide is 0.5%～60.0%, is preferably 10.0%～40.0%; In the zirconia modified inorganic refractory oxide, zirconic mass content is 0.1%～50.0%, is preferably 5.0%～30.0%.
Described rare earth modified molecular sieve is preferably the rare earth modified molecular sieve that hydrogen type molecular sieve obtains after rare earth modified.Described molecular screening one or more in beta-molecular sieve, Y zeolite, SAPO molecular sieve and ZSM type molecular sieve are preferably Y zeolite and/or ZSM type molecular sieve, more preferably Y zeolite.Rare earth of the present invention is selected from one or more in lanthanum, cerium, praseodymium and the neodymium, is preferably lanthanum or/and cerium, more preferably lanthanum.
Described inorganic refractory oxide is to be selected from aluminium oxide, titanium oxide, silica, boron oxide, magnesia, kaolin and the clay one or more, is preferably aluminium oxide and/or kaolin, more preferably aluminium oxide.
Preparation of catalysts method of the present invention comprises the steps:
(1), with rare earth loaded to molecular sieve, through super-dry and roasting, obtain rare earth modified molecular sieve;
(2), zirconium is loaded on the inorganic refractory oxide, through super-dry and roasting, obtain the modified zirconia inorganic refractory oxide;
(3), rare earth modified molecular sieve, zirconia modified inorganic refractory oxide, water and peptizing agent fully mixed pinch into plastic paste, extruded moulding through super-dry and roasting, obtains olefinic hydrocarbon expelling catalyzer of the present invention.
Rare earth loaded described in the step (1) can be adopted ion-exchange, infusion process or kneading method to molecular sieve, when wherein adopting ion-exchange or infusion process, the used compounds containing rare earth of solution that preparation contains rare earth are selected from one or more in oxide, chloride, nitrate, sulfate and the carbonate, be preferably and be selected from chloride and/or nitrate, more preferably nitrate.When adopting kneading method, be that compounds containing rare earth are fully mixed with molecular sieve, compounds containing rare earth are to be selected from oxide, chloride, nitrate, sulfate and the carbonate one or more, are preferably oxide and/or nitrate, more preferably oxide.
The described zirconium of step (2) loads on the inorganic refractory oxide and can adopt infusion process or kneading method, when wherein adopting infusion process, the used zirconium-containing compound of solution that preparation contains zirconium is to be selected from zirconium nitrate, zirconyl chloride, zirconium sulfate, zirconium oxysulfate, the zirconium iso-propoxide one or more, be preferably zirconium nitrate and/or zirconium chloride, more preferably zirconium nitrate.When adopting kneading method, be that zirconium-containing compound is fully mixed with the precursor of inorganic refractory oxide, wherein zirconium-containing compound is one or more in zirconia, zirconium nitrate, zirconyl chloride, zirconium sulfate, the zirconium oxysulfate, is preferably zirconium nitrate and/or zirconia, more preferably zirconia.Inorganic refractory oxide is to be selected from aluminium oxide, titanium oxide, silica, boron oxide, magnesia, kaolin and the clay one or more, be preferably aluminium oxide and kaolin, aluminium oxide more preferably, the precursor of aluminium oxide can be selected from boehmite, boehmite, diaspore, gibbsite and visit in the aluminium stone one or more.
The described peptizing agent of step (3) is inorganic acid or organic acid, is preferably inorganic acid, and more preferably hydrochloric acid and nitric acid most preferably are nitric acid; Wherein the mass concentration of used salpeter solution is 1.0%～30.0%, is preferably 1.0%～5.0%, and consumption expects to be as the criterion for plastic block can make to mix to pinch.Step (3) in order to be beneficial to extruded moulding, can adopt extrusion aid in the shaping of catalyst process, for example graphite, starch, cellulose and sesbania powder etc.
Drying condition described in step (1), (2) and (3) is normal temperature～300 ℃ maintenance 1h～48h, and step (1), step (2) and the described drying condition of step (3) can be identical, also can be different.The roasting condition of step (1) and (2) is 400 ℃～900 ℃ and keeps 0.5h～10.0h that step (1) can be identical with the described roasting condition of step (2), also can be different.The described catalyst roasting condition of step (3) is 300 ℃～600 ℃ and keeps 1h～8h.
The key component of catalyst of the present invention is rare earth modified molecular sieve and modified zirconia inorganic refractory oxide.Because in the rare earth modified molecular sieve process, rare earth element can act on the B acid position of molecular sieve, the acid strength of molecular sieve is reduced, and can produce more acid position, when providing more active sites for catalyst, avoided side reactions such as the coking of strong acidic site and carbon distribution, activity of such catalysts and stability all are significantly improved.Can produce a large amount of L acid sites through the modified zirconia inorganic oxide, the effect that is subjected to Electronic Performance can improve catalyst and aromatic hydrocarbons and alkene of L acid position, thereby the touch opportunity of active sites on increase reactant and the catalyst, the reactivity worth of raising catalyst.By the synergy of rare earth modified molecular sieve and modified zirconia inorganic refractory oxide, can improve activity of such catalysts and stability effectively.
Catalyst of the present invention can be used for catalytic refining reformed oil process, under conditions of non-hydrogen, the reformed oil raw material reacts through beds of the present invention, and reaction condition is as follows: reaction temperature is that 80 ℃～350 ℃, reaction pressure are that 0.01MPa～2.0MPa, volume space velocity are 0.5h
-1～40.0h
-1, obtain the reformed oil of deolefination.
Adopt catalyst of the present invention to make with extra care reformed oil, can remove trace amounts of olefin wherein effectively, make simultaneously that arene content has increase slightly in the product, have characteristics such as catalytic activity height, good stability, can satisfy the long-term operation requirement of device.
The specific embodiment
On the 20ml evaluating apparatus, carry out catalytic reforming and generate oily non-hydrogen catalytic refining test, loaded catalyst is 20ml (40～60 order), under nitrogen environment, catalyst is carried out 350 ℃ of preliminary treatment in 4 hours before the charging, reaction pressure is regulated with nitrogen, and 56 ℃～141 ℃ of feedstock oil boiling ranges, arene content are that (wherein benzene is 7.86m% to 70.79m%, toluene is 18.65m%, ethylbenzene is 20.03m%, and mixed xylenes is 12.79m%, C
9Aromatic hydrocarbons is 11.46m%), bromine index is 2702mgBr/100ml.Reaction condition is: 160 ℃ of reaction temperatures, pressure 1.0MPa, volume space velocity 20h
-1Feedstock oil, refined oil composition carry out quantitative analysis on the HP5890 gas chromatograph.Among the present invention, m% represents mass fraction.
The invention will be further described below by embodiment, but the present invention is not limited to this.
Embodiment 1
The preparation process of catalyst E-1 of the present invention is as follows:
(1) with 1000 gram mass concentration is the lanthanum nitrate hexahydrate and the 800 gram Hydrogen Y molecular sieve (SiO of 20% (in lanthana)
2/ Al
2O
3Mol ratio is 8.7, specific area 726m
2/ g) fully mix, under 130 ℃ of conditions dry 24 hours then, roasting was 3 hours under 750 ℃ of conditions, obtained the lanthana mass content and be 20% Modified Zeolite Y.
(2) be that the zirconium nitrate solution and 450 gram (in the aluminium oxide) aluminium hydroxides (SB that German Condean company produces) of 10% (in zirconia) fully mix with 500 gram mass concentration, under 50 ℃ of conditions dry 48 hours then, roasting is 8 hours under 400 ℃ of conditions, obtains the zirconia mass content and be 10% modified aluminas.
(3) modified aluminas that 220 Modified Zeolite Y that obtain of gram steps (1), 200 gram steps (2) are obtained and 10 gram sesbania powder mix, add 230ml water and 14ml red fuming nitric acid (RFNA) (mass concentration is 66.5%) then, fully mix and pinch, make it to become the paste plastic, extruding diameter on banded extruder is the cylinder bar of 1.5mm, the cylinder bar descended dry 16 hours at 100 ℃, and 550 ℃ of roastings obtained catalyst E-1 of the present invention in 4 hours in air atmosphere then.Consisting of of this catalyst sees Table 1, and evaluation result sees Table 2 and table 3.
Embodiment 2
The preparation of catalyst E-2 of the present invention
The preparation process of catalyst E-2 of the present invention is with embodiment 1, and difference is to replace lanthanum nitrate with cerous nitrate, and the composition of the catalyst E-2 of the present invention for preparing sees Table 1, and the product bromine index the results are shown in Table 2 and table 3.
Embodiment 3
The preparation of catalyst E-3 of the present invention
The preparation process of catalyst E-3 of the present invention is with embodiment 1, and difference is with Hydrogen ZSM-5 molecular sieve (SiO
2/ Al
2O
3Mol ratio is 58, specific area 276m
2/ g) replacing the Hydrogen Y zeolite, the composition E-3 of the catalyst of preparing of the present invention sees Table 1, and the product bromine index the results are shown in Table 2 and table 3.
Embodiment 4
The preparation of catalyst E-4 of the present invention
The preparation process of catalyst E-4 of the present invention is with embodiment 1, and difference is that used refractory aluminium oxide is the mixture of kaolin and aluminium oxide, and the composition of the catalyst E-4 of the present invention for preparing sees Table 1, and the product bromine index the results are shown in Table 2 and table 3.
Embodiment 5～8
The preparation of catalyst E-5～E-8 of the present invention
The preparation process of catalyst E-5～E-8 of the present invention is with embodiment 1, and the amount of the used lanthanum nitrate of difference, molecular sieve, zirconium nitrate and aluminium hydroxide is different, and the composition of the catalyst E-5～E-8 of the present invention for preparing sees Table 1, and the product bromine index the results are shown in Table 2 and table 3.
Comparative Examples 1
The preparation of contrast medium C-1 of the present invention
According to CN200410046820.0 embodiment 1 disclosed method, promptly catalyst adopts aluminium stone and beta molecular sieve (SiO
2/ Al
2O
3Mol ratio is 26, specific area 547m
2/ g) obtaining contrast medium C-1 through extrusion, drying and roasting, it consists of: molecular sieve mass content 50%, surplus are aluminium oxide, result of the test sees Table 2 and table 3.
The composition of table 1 catalyst
| Catalyst | Re 2O 3 ①/ molecular sieve ②，m％ | ZrO 2 ③/ refractory oxide ④，m％ |
| E-1 | 20.0/55.0 | 10.0/ surplus |
| E-2 | 20.0 ⑤/55.0 | 10.0/ surplus |
| E-3 | 20.0/55.0 ⑥ | 10.0/ surplus |
| E-4 | 20.0/55.0 | 10.0/ surplus ⑦ |
| E-5 | 35.0/30.0 | 15.0/ surplus |
| E-6 | 30.0/60.0 | 20.0/ surplus |
| E-7 | 15.0/70.0 | 25.0/ surplus |
| E-8 | 12.0/80.0 | 28.0/ surplus |
| C-1 | 0/55.0 | 0/ surplus |
Annotate: do not have dated Re in the table 1
2O
3Be lanthana, molecular sieve is a Y zeolite, and refractory oxide is an aluminium oxide.1. with respect to modified molecular screen; 2. with respect to catalyst; 3. with respect to the modified inorganic refractory oxide; 4. with respect to catalyst; 5. cerium oxide; 6. ZSM-5; 7. 30% kaolin and surplus aluminium oxide.
The result of bromine index in the table 2 differential responses time refined oil
The result of table 2 shows that it is active and better stable that catalyst of the present invention has the deolefination higher than contrast medium.
Arene content when table 3 adopts different catalysts in the refined oil
| Embodiment | The catalyst numbering | Arene content, m% | Arene content changes, m% |
| 1 | E-1 | 72.34 | +1.55 |
| 2 | E-2 | 71.36 | +0.56 |
| 3 | E-3 | 72.20 | +1.41 |
| 4 | E-4 | 71.56 | +0.77 |
| 5 | E-5 | 71.09 | +0.30 |
| 6 | E-6 | 71.28 | +0.49 |
| 7 | E-7 | 72.81 | +2.02 |
| 8 | E-8 | 73.08 | +2.29 |
| Comparative Examples 1 | C-1 | 70.94 | +0.15 |
Annotate: the sample when above-mentioned sample is reaction 2h, positive number represent that aromatic hydrocarbons increases, the loss of negative number representation aromatic hydrocarbons.
The result of table 3 shows, adopts in the technology of the present invention process, and aromatic hydrocarbons is not loss not only, and has increase in various degree.
This shows that adopt catalyst of the present invention to make with extra care reformed oil, life of catalyst and stability then substantially exceed correlation technique, aromatic hydrocarbons is not loss not only, and has increase in various degree, significantly is better than correlation technique.
Claims (14)
1. olefinic hydrocarbon expelling catalyzer, form by rare earth modified molecular sieve and zirconia modified inorganic refractory oxide, quality with catalyst is a benchmark, and the content of rare earth modified molecular sieve is 1.0%～99.0%, and the content of zirconia modified inorganic refractory oxide is 1.0%～99.0%; In the wherein said rare earth modified molecular sieve, the mass content of rare earth oxide is 0.5%～60.0%; In the described zirconia modified inorganic refractory oxide, zirconic mass content is 0.1%～50.0%; The described rare earth modified molecular sieve rare earth modified molecular sieve that to be hydrogen type molecular sieve obtain after rare earth modified; Described molecular sieve is to be selected from beta-molecular sieve, Y zeolite, SAPO molecular sieve and the ZSM type molecular sieve one or more.
2. according to the described catalyst of claim 1, it is characterized in that, is benchmark with the quality of catalyst, and the content of rare earth modified molecular sieve is 51.0%～80.0%, and the content of zirconia modified inorganic refractory oxide is 20.0%～49.0%.
3. according to claim 1 or 2 described catalyst, it is characterized in that in the described rare earth modified molecular sieve, the mass content of rare earth oxide is 10.0%～40.0%.
4. according to claim 1 or 2 described catalyst, it is characterized in that zirconic mass content is 5.0%～30.0% in the described zirconia modified inorganic refractory oxide.
5. according to the described catalyst of claim 1, it is characterized in that described molecular sieve is Y zeolite and/or ZSM type molecular sieve.
6. according to the described catalyst of claim 1, it is characterized in that described rare earth is selected from one or more in lanthanum, cerium, praseodymium and the neodymium.
7. according to the described catalyst of claim 1, it is characterized in that described rare earth is selected from lanthanum or/and cerium.
8. according to the described catalyst of claim 1, it is characterized in that described inorganic refractory oxide is to be selected from aluminium oxide, titanium oxide, silica, boron oxide and the magnesia one or more.
9. according to the described catalyst of claim 1, it is characterized in that described inorganic refractory oxide is an aluminium oxide.
10. the arbitrary described Preparation of catalysts method of claim 1～9 comprises the steps:
(1), with rare earth loaded to molecular sieve, through super-dry and roasting, obtain rare earth modified molecular sieve;
(2), zirconium is loaded on the inorganic refractory oxide, through super-dry and roasting, obtain zirconia modified inorganic refractory oxide;
(3), rare earth modified molecular sieve, zirconia modified inorganic refractory oxide, water and peptizing agent fully mixed pinch into plastic paste, extruded moulding through super-dry and roasting, obtains described olefinic hydrocarbon expelling catalyzer.
11. in accordance with the method for claim 10, it is characterized in that rare earth loaded described in the step (1) adopt ion-exchange, infusion process or kneading method to molecular sieve; The described zirconium of step (2) loads to and adopts infusion process or kneading method on the inorganic refractory oxide.
12. in accordance with the method for claim 10, it is characterized in that the drying condition described in step (1), (2) and (3) is normal temperature～300 ℃ maintenance 1h～48h; The roasting condition of step (1) and (2) is 400 ℃～900 ℃ and keeps 0.5h～10.0h; In the step (3), the catalyst roasting condition is 300 ℃～600 ℃ and keeps 1h～8h.
13. the method for a catalytic refining reformed oil under conditions of non-hydrogen is characterized in that adopting claim 1 to the arbitrary described catalyst of claim 9.
14. in accordance with the method for claim 13, the process that it is characterized in that catalytic refining reformed oil under conditions of non-hydrogen is as follows: reformed oil is through described beds, the deolefination reaction takes place under conditions of non-hydrogen, and reaction condition is as follows: reaction temperature is that 80 ℃～350 ℃, reaction pressure are that 0.01MPa～2.0MPa, volume space velocity are 0.5h
-1～40.0h
-1, obtain the reformed oil of deolefination.
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| CN103055935A (en) * | 2012-12-16 | 2013-04-24 | 青岛博益特生物材料有限公司 | Hydro-catalyst |
| CN109433250A (en) * | 2018-10-16 | 2019-03-08 | 江苏华伦化工有限公司 | Reduce the catalyst of high boiling aromatic hydrocarbon solvent bromine index |
| 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 |
| CN110813370B (en) * | 2019-10-29 | 2022-05-24 | 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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|---|---|---|---|---|
| US3647916A (en) * | 1969-10-08 | 1972-03-07 | Mobil Oil Corp | Isoparaffin-olefin alkylation with crystalline zeolite catalysts at low isoparaffin to olefin ratios |
| CN1506161A (en) * | 2002-12-13 | 2004-06-23 | 中国石油天然气股份有限公司 | Ultrastable rare earth Y molecular sieve active component and preparation method thereof |
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2010
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US3647916A (en) * | 1969-10-08 | 1972-03-07 | Mobil Oil Corp | Isoparaffin-olefin alkylation with crystalline zeolite catalysts at low isoparaffin to olefin ratios |
| CN1506161A (en) * | 2002-12-13 | 2004-06-23 | 中国石油天然气股份有限公司 | Ultrastable rare earth Y molecular sieve active component and preparation method thereof |
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| Title |
|---|
| "ZrO2-Al2O3催化剂载体的制备及应用";高晓等;《工业催化》;20080315;第16卷(第3期);第3，4节 * |
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