CN105709810A - C5C6 isomerization catalyst and preparation method thereof - Google Patents
C5C6 isomerization catalyst and preparation method thereof Download PDFInfo
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- CN105709810A CN105709810A CN201410723154.3A CN201410723154A CN105709810A CN 105709810 A CN105709810 A CN 105709810A CN 201410723154 A CN201410723154 A CN 201410723154A CN 105709810 A CN105709810 A CN 105709810A
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Abstract
The invention relates to a C5C6 isomerization catalyst. The catalyst has a specific surface area of greater than 280 m<2>/g, bulk density of 0.55 to 0.65 g/ml and strength of 121 to 146 N/cm<2>, wherein a mol ratio of silicon oxide to alumina, i.e., a silica-alumina ratio, is 18 to 48. The invention also provides a preparation method for the C5C6 isomerization catalyst. The C5C6 isomerization catalyst directly prepared from high-silicon mordenite through one-shot ammonium exchange omits the procedures of acid exchange for three times and ammonium exchange for one time for a carrier in the prior art, has good isomerization performance and is energy-saving and environment-friendly.
Description
Technical field
The invention belongs to light paraffins isomerization field, be specifically related to a kind of C5C6 isomerization catalyst and preparation method thereof.
Background technology
Modenite (NaM type zeolite) is the molecular sieve that a kind of silica alumina ratio is higher, and its structural formula is Na [Al8Si40O96]·24H2O, has substantial amounts of five-membered ring, and parallel with one another in couples, and main aperture road is straight-cylindrical twelve-ring, and aperture ellipsoidal cross section is of a size of 0.65 × 0.68nm, can be expanded further by modified hole.
The former powder of modenite adopting conventional method synthesis is sodium form modenite (NaM), silica alumina ratio about 10, catalysis activity is relatively low, it usually needs carry out repeatedly ammonium exchange and NaM is converted into the h-mordenite (HM) with relatively high silica alumina ratio by acid exchange.Needed for market, modenite mostly is silica alumina ratio HM more than 18, it usually needs exchange more than four times repeatedly, in each exchange process, also need to carry out to wash, filter, the step such as drying, complicated operation, expend substantial amounts of hydrochloric acid simultaneously, not only increase cost, etching apparatus, also result in environmental pollution.
The Catalysts and its preparation method of a kind of hydroisomerization reaction suitable in C5C6 n-alkane disclosed in Chinese patent 99105790.2 " catalyst for isomerizing light hydrocarbon and preparation method thereof "；During a kind of isomerization reaction for catalysis normal hexane pentane, activity is higher disclosed in the Chinese patent 201410075578.3 " the C5C6 alkane isomerization catalyst of load nickel borides and preparation and application thereof ", isoparaffin selectivity and the good Catalysts and its preparation method of stability and application；The Catalysts and its preparation method of a kind of better activity stability and isomerisation selectivity disclosed in the Chinese patent 03122849.6 " a kind of low-carbon alkanes isomerization catalyst and preparation method "；All also exist cost of material height, processing step complicated, frequently acid exchange affect the internal structure of modenite, the problem causing activity decrease；Synthesizing field at modenite, the research being directly synthesized high silicon mordenite becomes heat subject in recent years.
Summary of the invention
It is an object of the invention to provide a kind of high silicon mordenite being directly synthesized and make C5C6 isomerization catalyst and preparation method thereof through an ammonium exchange.
The technical scheme realizing the object of the invention is a kind of C5C6 isomerization catalyst, and the specific surface area of this catalyst is more than 280m2/ g, bulk density is 0.55-0.65g/ml, and intensity is 121-146N/cm2, the wherein mol ratio of silica/alumina and silica alumina ratio 18-48.
The mol ratio of preferential wherein silica/alumina and silica alumina ratio 31-48.
A kind of preparation method of C5C6 isomerization catalyst, comprise the following steps: that (1) first prepares high silicon mordenite and aluminium sesquioxide weight ratio between 50:50-95:5, silica alumina ratio carrier between 18-48, concrete operations are by dust technology silk union geolyte and aluminium sesquioxide powder, extrusion molding, drying and calcination process；(2) prepared shaping carrier is carried out evacuation process；(3) carrier after step 2 being processed adds active ingredient solution；(4) by the prepared thing reflow treatment of step 3, active component is allowed to be sufficiently submerged in catalytic inner；(5) undertaken the gains of step 4 drying and making C5C6 isomerization catalyst after calcination process.
Dry duration 5-12h in preferred step 1, calcination process is roasting 3-8h at 300-600 DEG C.
In preferred step 2, shaping carrier is bar shaped carrier, the duration 0.1-4h that evacuation processes.
In preferred step 3, the component of active ingredient solution includes: by weight, if catalyst is 1, active metal is 0.1-1%, and hydrochloric acid is 2.5-8.5%, and nitric acid is 2.5-8.5%, and adsorbent is 2-10%.
Active metal described in preferred step 3 is selected from Pt or Pd, described Pt or Pd 0.1-0.3% by weight；Described adsorbent is selected from acetic acid, maleic acid, oxalic acid, trichloroacetic acid or citric acid.
It is backflow 1-8h in condensation reflux unit that condensing reflux described in preferred step 4 processes, temperature 100-110 DEG C.
Drying in preferred step 5 is at 100-120 DEG C, and required duration 4-12h, roasting is at 400-600 DEG C, required duration 4-8h.
The present invention has positive effect: this method adopts the high silicon mordenite that is directly synthesized to be that carrier passes through an ammonium exchange and makes C5C6 isomerization catalyst, eliminate three subacid exchanges of the prior art and an ammonium exchange, isomerization performance is good, reduce cost and labor intensity, decrease the pollution with environment of the corrosion to equipment, there is higher Social and economic benef@.
Detailed description of the invention
The specific surface area of this C5C6 isomerization catalyst is more than 280m2/ g, bulk density is 0.55-0.65g/ml, and intensity is 121-146N/cm2, the wherein mol ratio of silica/alumina and silica alumina ratio 18-48；This catalyst initial lifetime 2 years, after regeneration, the life-span was up to 5 years.
Embodiment 1:(1) first to prepare high silicon mordenite and aluminium sesquioxide weight ratio be 50:50, the carrier of silica alumina ratio 18, concrete operations are that dry 12h, at 600 DEG C of roasting 3h by dust technology silk union geolyte and aluminium sesquioxide powder, extruded moulding；(2) prepared bar shaped carrier is carried out evacuation and processes 0.1h；(3) carrier after step 2 being processed adds active ingredient solution, the component of active ingredient solution by weight 0.1% Pd solution (Palladous chloride. is dissolved in dilute hydrochloric acid or ammonia), the hydrochloric acid of 5.5%, the nitric acid of 3.5%, the trichloroacetic acid of 4.5%；(4) reflux 8h by the gained solidliquid mixture of step 3 in condensation reflux unit, and temperature is 100 DEG C；(5) solid after the reflow treatment of step 4 is dried 12h at 100 DEG C, after 600 DEG C of roasting 4h, make C5C6 isomerization catalyst A.
Embodiment 2:(1) first to prepare high silicon mordenite and aluminium sesquioxide weight ratio be 75:25, the carrier of silica alumina ratio 31, concrete operations are that dry 8h, at 600 DEG C of roasting 4h by dust technology silk union geolyte and aluminium sesquioxide powder, extruded moulding；(2) prepared bar shaped carrier is carried out evacuation and processes 4h；(3) carrier after step 2 being processed adds active ingredient solution, the component of active ingredient solution by weight 0.3% Pd solution (Palladous chloride. is dissolved in dilute hydrochloric acid or ammonia), the hydrochloric acid of 5.5%, the nitric acid of 3.5%, the trichloroacetic acid of 6.5%；(4) reflux 1h by the gained solidliquid mixture of step 3 in condensation reflux unit, and temperature is 110 DEG C；(5) solid after the reflow treatment of step 4 is dried 4h at 120 DEG C, after 400 DEG C of roasting 8h, make C5C6 isomerization catalyst B.
Embodiment 3:(1) first to prepare high silicon mordenite and aluminium sesquioxide weight ratio be 95:5, the carrier of silica alumina ratio 48, concrete operations are that dry 5h, at 300 DEG C of roasting 8h by dust technology silk union geolyte and aluminium sesquioxide powder, extruded moulding；(2) prepared bar shaped carrier is carried out evacuation and processes 4h；(3) carrier after step 2 being processed adds active ingredient solution, the component of active ingredient solution by weight 0.55% Pd solution (Palladous chloride. is dissolved in dilute hydrochloric acid or ammonia), the hydrochloric acid of 2.5%, the nitric acid of 5.5%, the trichloroacetic acid of 7.5%；(4) reflux 6h by the gained solidliquid mixture of step 3 in condensation reflux unit, and temperature is 110 DEG C；(5) solid after the reflow treatment of step 4 is dried 12h at 110 DEG C after 500 DEG C of roasting 4h, make C5C6 isomerization catalyst C.
Adopt pressure microreactor that C5C6 isomerization catalyst A, B, C of making are carried out light hydrocarbon isomerization reaction test: raw material: pentane (analytical pure): Shanghai Fei Da Trade Co., Ltd. and the pentane 99.7% of bridge branch company, isopentane 0.3%；Normal hexane (analytical pure): Shanghai Fei Da Trade Co., Ltd. and the normal hexane 96% of bridge branch company, aromatic hydrocarbons 0.2%, all the other isohexanes；Reaction condition is as follows: reaction temperature: 260 DEG C；Pressure: 2Mpa；Air speed: 2h-1；Hydrogen-oil ratio: 8 (mol ratios)；Computing formula is as follows:
Result of the test is as shown in the table: wherein
2MP 2-methylpentane；3MP 3-methylpentane；NC5Pentane；NC6Normal hexane；
2,2DMB 2,2-dimethylbutane；MCP methyl cyclopentane
The C5C6 isomerization catalyst silica alumina ratio made is between 18-48, and C5C6 isomerization has higher activity and selectivity, and isomerization performance is better, and the C5C6 isomerization performance of the high silicon mordenite being directly synthesized meets or exceeds low silicon content mordenite.
Particular embodiments described above; the purpose of the present invention, technical scheme and beneficial effect have been further described; it is it should be understood that; the foregoing is only specific embodiments of the invention; it is not limited to the present invention; all within the spirit and principles in the present invention, any amendment of making, equivalent replacement, improvement etc., should be included within protection scope of the present invention.
Claims (9)
1. a C5C6 isomerization catalyst, it is characterised in that: the specific surface area of this catalyst is more than 280m2/ g, bulk density is 0.55-0.65g/ml, and intensity is 121-146N/cm2, the wherein mol ratio of silica/alumina and silica alumina ratio 18-48.
2. C5C6 isomerization catalyst according to claim 1, it is characterised in that: the wherein mol ratio of silica/alumina and silica alumina ratio 31-48.
3. the preparation method of C5C6 isomerization catalyst described in a claim 1 or 2, comprise the following steps: that (1) first prepares high silicon mordenite and aluminium sesquioxide weight ratio between 50:50-95:5, silica alumina ratio carrier between 18-48, concrete operations are by dust technology silk union geolyte and aluminium sesquioxide powder, extrusion molding, drying and calcination process；(2) prepared shaping carrier is carried out evacuation process；(3) carrier after step 2 being processed adds active ingredient solution；(4) by the prepared thing reflow treatment of step 3, active component is allowed to be sufficiently submerged in catalytic inner；(5) undertaken the gains of step 4 drying and making C5C6 isomerization catalyst after calcination process.
4. the preparation method of C5C6 isomerization catalyst according to claim 3, it is characterised in that: dry duration 5-12h in step 1, calcination process is roasting 3-8h at 300-600 DEG C.
5. the preparation method of C5C6 isomerization catalyst according to claim 3, it is characterised in that: in step 2, shaping carrier is bar shaped carrier, the duration 0.1-4h that evacuation processes.
6. the preparation method of C5C6 isomerization catalyst according to claim 3, it is characterised in that: in step 3, the component of active ingredient solution includes: by weight, if catalyst is 1, active metal is 0.1-1%, hydrochloric acid is 2.5-8.5%, and nitric acid is 2.5-8.5%, and adsorbent is 2-10%.
7. the preparation method of C5C6 isomerization catalyst according to claim 6, it is characterised in that: described active metal is selected from Pt or Pd, described Pt or Pd 0.1-0.3% by weight；Described adsorbent is selected from acetic acid, maleic acid, oxalic acid, trichloroacetic acid or citric acid.
8. the preparation method of C5C6 isomerization catalyst according to claim 3, it is characterised in that: it is backflow 1-8h in condensation reflux unit that the condensing reflux described in step 4 processes, temperature 100-110 DEG C.
9. the preparation method of C5C6 isomerization catalyst according to claim 3, it is characterised in that: drying in step 5 is at 100-120 DEG C, and required duration 4-12h, roasting is at 400-600 DEG C, required duration 4-8h.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106732753A (en) * | 2016-11-16 | 2017-05-31 | 中国海洋石油总公司 | The preparation method of temp isomerizing catalyst in a kind of C5, C6 |
| CN113600226A (en) * | 2021-08-30 | 2021-11-05 | 南京克米斯璀新能源科技有限公司 | Heavy alkylbenzene anti-alkylation catalyst and preparation method and application thereof |
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| US3836597A (en) * | 1972-04-25 | 1974-09-17 | Shell Oil Co | Hydrocarbon isomerization process |
| CN87103444A (en) * | 1987-04-29 | 1988-11-30 | 环球油品公司 | Composite catalyst for paraffin isomerization |
| US4899012A (en) * | 1988-10-17 | 1990-02-06 | Uop | Catalyst for the isomerization of aromatics |
| CN1044053A (en) * | 1989-01-13 | 1990-07-25 | 中国石油化工总公司石油化工科学研究院 | Alkyl aromatic hydrocarbon isomerization catalyst and preparation method thereof |
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2014
- 2014-12-03 CN CN201410723154.3A patent/CN105709810A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US3836597A (en) * | 1972-04-25 | 1974-09-17 | Shell Oil Co | Hydrocarbon isomerization process |
| CN87103444A (en) * | 1987-04-29 | 1988-11-30 | 环球油品公司 | Composite catalyst for paraffin isomerization |
| US4899012A (en) * | 1988-10-17 | 1990-02-06 | Uop | Catalyst for the isomerization of aromatics |
| CN1044053A (en) * | 1989-01-13 | 1990-07-25 | 中国石油化工总公司石油化工科学研究院 | Alkyl aromatic hydrocarbon isomerization catalyst and preparation method thereof |
Non-Patent Citations (1)
| Title |
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| 韩松，施力，鲁国正，郜臣，: "Pd/丝光沸石C5/C6异构化催化剂研制", 《中国石油学会第五届石油炼制学术年会论文集》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106732753A (en) * | 2016-11-16 | 2017-05-31 | 中国海洋石油总公司 | The preparation method of temp isomerizing catalyst in a kind of C5, C6 |
| CN106732753B (en) * | 2016-11-16 | 2019-08-27 | 中国海洋石油集团有限公司 | The preparation method of temp isomerizing catalyst in a kind of C5, C6 |
| CN113600226A (en) * | 2021-08-30 | 2021-11-05 | 南京克米斯璀新能源科技有限公司 | Heavy alkylbenzene anti-alkylation catalyst and preparation method and application thereof |
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