CN103230788A - Refining catalyst for removing olefin in reformate - Google Patents
Refining catalyst for removing olefin in reformate Download PDFInfo
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- CN103230788A CN103230788A CN2013101762741A CN201310176274A CN103230788A CN 103230788 A CN103230788 A CN 103230788A CN 2013101762741 A CN2013101762741 A CN 2013101762741A CN 201310176274 A CN201310176274 A CN 201310176274A CN 103230788 A CN103230788 A CN 103230788A
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- reformate
- refining
- catalyst
- carclazyte
- olefinic hydrocarbon
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Abstract
The invention provides a refining catalyst for removing the olefin in reformate. The refining catalyst comprises the following components by mass percent: 60-90% of ordinary carclazyte and 5-40% of silicon-modified aluminium hydroxide dry glue and/or amorphous silicon aluminium and also comprises the following components according to the element mass fraction: 0.01-2.00% of at least one element of Cl, S and P and alumina-sol aqueous solution with the content of aluminium oxide being 0-30%. The refining catalyst provided by the invention can be used for removing trace olefin in the reformate, has better activity and stability, and can be regenerated by 1-2 times, so that the treated amount of the waste carclazyte catalyst and the pollution to the environment are reduced.
Description
Technical field
The present invention relates to a kind of reformate catalyst for refining.
Background technology
Aromatic hydrocarbons is the important foundation raw material of petrochemical industry industry, and wherein benzene,toluene,xylene (BTX aromatic hydrocarbons) is called as the one-level Organic Ingredients, occupies an important position in petrochemicals.Aromatic hydrocarbons is mainly derived from naphtha steam cracking device and catalytic reforming unit.Contain certain impurity such as alkene in the reformate, comprise monoolefine, alkadienes and colloid etc.These impurity have a negative impact to aromatic hydrocarbons later separation and processing and properties of product, must remove before entering separator.At present, remove that trace amounts of olefin has hydrofinishing and non-hydrogenation method in the reformate.Hydro-refining unit investment is big, complex process, energy consumption height, the at present industrial non-hydrogenation technology that adopt more.Non-hydrogen addition technology has clay-filtered adsorption refining and molecular sieve catalytic adsorption refining technology.
Carclazyte has catalyzed alkene and diene polymerization activity, thereby makes trace amounts of olefin polycondensation in the reformate and be adsorbed in its duct.Advantages such as clay-filtered technology has that the carclazyte raw material is easy to get, high adsorption capacity, low price, device are simple, easy to operate, but exist the cycle of operation short, change problems such as frequent.Chinese invention patent CN102658196A discloses a kind of preparation method of molecular sieve modified clay catalyst, and the modified argil catalyst of this method preparation is 60～80% atlapulgites and two or more component 10～20% lewis acid catalysts, 5～20% molecular sieves or 0.5～5% rare earth chloride by weight.
Molecular sieve catalyst has advantages such as deolefination is active high, and the cycle of operation is long.Disclose a kind of catalyst that removes trace amounts of olefin in the aromatic hydrocarbons as Chinese patent CN101433856A, this catalyst contains the aluminium oxide of 30-70% (quality), the molecular sieve of 30-70% (quality), lanthanide rare, P, W, Nb or the Mo of 0-40% (quality).
Chinese patent CN102069008A discloses a kind of catalyst that removes alkene in the reformation aromatic hydrocarbons, and this catalyst contains the modification REY molecular sieve of the phosphorous or amorphous silicon oxide of the MCM series molecular sieve of 20-80% (quality) and 20-80% (quality).
Chinese patent CN101992117A discloses a kind of reformate olefinic hydrocarbon expelling catalyzer, this catalyst contains the 20-90% molecular sieve, 10-80%SiO2, Al2O3 or its mixture, Ni, the Mo, Zr, Nb metal or its oxide that contain 0.1-10% simultaneously, 0.01-2.00%Cl, Br, S element or its oxide, 0.05-5%F, P element or its oxide.
The catalyst price that removes alkene in the reformation aromatic hydrocarbons of above patent disclosure is all very high, is generally clay-filtered dose 15-20 doubly, and its use is restricted.
Summary of the invention
Technical problem to be solved by this invention is for overcoming the deficiency that prior art exists, a kind of modified argil reformate catalyst for refining being provided.This catalyst has the active height of deolefination, operation cycle length, recyclable regenerative 1～2 time, lower-price characteristic.
The present invention solves its technical problem by the following technical programs: the reformate catalyst for refining that provides, comprise 60～90% common carclazyte, 5～40% aluminum hydroxide solid elastomers and/or amorphous silicon aluminium compound, the Cl of 0.01-2.00%, the aluminium oxide of S or P element and 0-30%, above percentage is mass percent, the percentage sum of each component is 100%, above-mentioned substance mixes, pinch through overmulling, extrusion, dry, processes such as roasting make, wherein, baking temperature is 100-150 ℃, be 1-6 hour drying time, and sintering temperature is 120～400 ℃, roasting time is 2-6 hour; Preferred baking temperature is 100-120 ℃, and be 2-4 hour drying time; Preferred sintering temperature is 150～200 ℃, and roasting time is 3-4 hour.Cl, S or P element add with element compound aqueous solution form, and its element compound is hydrochloric acid, sulfuric acid or phosphoric acid; Aluminium oxide is the form adding with aluminium colloidal sol.
With the refining and removing olefin from aromatic hydrocarbon catalyst of the present invention preparation at 170 ℃, 1.0MPa, mass space velocity 30h
-1Estimate under the condition.
The present invention's beneficial effect compared with prior art is: carclazyte (or granular carclazyte) the reformate catalyst for refining that uses on the commercial plant is compared at present, the refining activity of deolefination and life-span have obviously been improved, and this catalyst for refining can be by straightforward procedure 1-2 the use of regenerating, reduce useless clay treatment amount, had tangible economic benefit and environmental benefit.This catalyst is compared with the refining olefinic hydrocarbon expelling catalyzer of molecular sieve, and price is its 15-20/one only, has reduced factory's one-time investment, has obvious economic benefit.
The specific embodiment
Be further elaborated below by the present invention of embodiment.
[embodiment 1]
Get common carclazyte 80g and 20g aluminum hydroxide solid elastomer (silica content 5%) and mix, add 40g water and mix, mix and pinch, extrusion, dry 2h under 120 ℃, 180 ℃ of following roasting 4h make catalyst B T-1.
[embodiment 2]
Get common carclazyte 70g and 30g aluminum hydroxide solid elastomer (silica content 5%) and mix, add 40g water and mix, mix and pinch, extrusion, dry 2h under 120 ℃, 180 ℃ of following roasting 4h make catalyst B T-2.
[embodiment 3]
Get common carclazyte 70g and 30g aluminum hydroxide solid elastomer (silica content 0%) and mix, add 40g water and mix, mix and pinch, extrusion, dry 2h under 120 ℃, 180 ℃ of following roasting 4h make catalyst B T-2.
[embodiment 4]
Get common carclazyte 70g and 30g amorphous silicon aluminium compound (silica content 20%) mixes, add 40g water and mix, mix and pinch, extrusion, at 120 ℃ of dry 2h down, 180 ℃ of following roasting 3h make catalyst B T-3.
[embodiment 5]
Getting common carclazyte 70g and 30g aluminum hydroxide solid elastomer (silica content 5%) mixes, it is even to add 60g solid content (in aluminium oxide quality mark) and be 25% aluminium colloidal sol aqueous solution, mixes and pinches extrusion, dry 2h under 120 ℃, 150 ℃ of following roasting 3h make catalyst B T-4.
[embodiment 6]
Getting common carclazyte 70g and 30g aluminum hydroxide solid elastomer (silica content 5%) mixes, mass fraction is 10% hydrochloric acid 1.4g and 40g water wiring solution-forming, mixed solution added in the solid mixture mix, mix and pinch, extrusion, dry 2h under 120 ℃, 150 ℃ of following roasting 3h make catalyst B T-5.
[embodiment 7]
Getting common carclazyte 70g and 30g aluminum hydroxide solid elastomer (silica content 5%) mixes, mass fraction is 58% sulfuric acid 2.7g and 40g water wiring solution-forming, mixed solution added in the solid mixture mix, mix and pinch, extrusion, dry 2h under 120 ℃, 150 ℃ of following roasting 3h make catalyst B T-6.
[embodiment 8]
Getting common carclazyte 70g and 30g aluminum hydroxide solid elastomer (silica content 5%) mixes, mass fraction is 85% phosphatase 11 .8g and 40g water wiring solution-forming, mixed solution added in the solid mixture mix, mix and pinch, extrusion, dry 2h under 120 ℃, 150 ℃ of following roasting 3h make catalyst B T-7.
[embodiment 9]
Getting common carclazyte 70g and 30g aluminum hydroxide solid elastomer (silica content 5%) mixes, mass fraction is that 10% hydrochloric acid 1.4g and 60g solid content (in aluminium oxide quality mark) are that 25% aluminium colloidal sol aqueous solution is even, mixed solution added in the solid mixture mix, mix and pinch, extrusion, dry 2h under 120 ℃, 150 ℃ of following roasting 3h make catalyst B T-8.
[embodiment 10]
Getting common carclazyte 70g and 30g aluminum hydroxide solid elastomer (silica content 5%) mixes, mass fraction is that 58% sulfuric acid 2.7g and 60g solid content (in aluminium oxide quality mark) are that 25% aluminium colloidal sol aqueous solution is even, mixed solution added in the solid mixture mix, mix and pinch, extrusion, dry 2h under 120 ℃, 150 ℃ of following roasting 3h make catalyst B T-9.
[embodiment 11]
Getting common carclazyte 70g and 30g aluminum hydroxide solid elastomer (silica content 5%) mixes, mass fraction is that 85% phosphatase 11 .8g and 60g solid content (in aluminium oxide quality mark) are that 25% aluminium colloidal sol aqueous solution is even, mixed solution added in the solid mixture mix, mix and pinch, extrusion, dry 2h under 120 ℃, 150 ℃ of following roasting 3h make catalyst B T-10.
[comparative example 1]
Carry out property comparison with the industrial atlapulgite that uses as the catalyst of catalyst and invention.Atlapulgite be numbered BT.
[contrast experiment]
With the catalyst that makes among the embodiment 1～10 and the experiment that removes of comparative example 1 being carried out trace amounts of olefin in the aromatic hydrocarbons in the 10ml fixed bed reactors, feedstock oil is Dalian petrochemical industry reformate, and about bromine index 540mgBr/100g oil, reaction pressure is 1.0MPa, 170 ℃ of temperature, air speed 30h
-1Catalyst activity calculates with the olefin removal rate, and regulation olefin removal rate is namely thought catalysqt deactivation less than 50%, gets a sample analysis every 1h, and olefin removal rate computing formula is as follows:
The catalyst of each embodiment preparation and the evaluation result of contrast medium see Table 1.
The catalyst of each embodiment preparation of table 1 and the olefin removal rate of contrast medium
From evaluation result as can be seen, prepared activity of such catalysts and the operation cycle of each embodiment all obviously is better than common clay catalyst.The prepared catalyst of modified argil reformate catalyst for refining preparation method that this patent provides has deolefination performance preferably.
[embodiment 12]
Embodiment 9 prepared BT-9 modified argil catalyst are carried out inactivation regeneration handle, 450 ℃ burn 3h regeneration in Muffle furnace, and carry out regenerating and modifying clay catalyst performance evaluation by embodiment 11.The regeneration evaluating data sees Table 2.
Table 2 catalyst regeneration evaluating data
The modified argil catalyst has regenerability preferably as can be seen from Table 2, renewable 1～2 time.
Claims (7)
1. a reformate is made with extra care olefinic hydrocarbon expelling catalyzer, it is characterized in that being formed by Cl, the S of 60～90% common carclazyte, 5～40% aluminum hydroxide solid elastomers and/or amorphous silicon aluminium compound, 0.01-2.00% or P element and 0-30% aluminium oxide, above percentage is mass percent, and the percentage sum of each component is 100%.
2. according to the refining olefinic hydrocarbon expelling catalyzer of the described reformate of claim 1, it is characterized in that described aluminum hydroxide solid elastomer is the ordinary hydrogen alumina dry glue, or Different Silicon content modified aluminum hydroxide solid elastomer.
3. according to the refining olefinic hydrocarbon expelling catalyzer of the described reformate of claim 1, it is characterized in that described Cl, S or P element compound are hydrochloric acid, sulfuric acid or phosphoric acid.
4. according to the refining olefinic hydrocarbon expelling catalyzer of the described reformate of claim 1, the content that it is characterized in that described common carclazyte is 65～80%, and the content of aluminum hydroxide solid elastomer and/or amorphous silicon aluminium compound is 20～35%.
5. according to described each the preparation method of the refining olefinic hydrocarbon expelling catalyzer of reformate of claim 1 to 4, it is characterized in that common carclazyte and aluminum hydroxide solid elastomer and/or amorphous aluminum silicide are mixed, add the aqueous solution contain Cl, S or P element compound and mass concentration then and be 25% aluminium colloidal sol, pinch through mixing, extrusion, drying and roasting and make.
6. according to the preparation method of the refining olefinic hydrocarbon expelling catalyzer of the described reformate of claim 5, it is characterized in that baking temperature is 100-150 ℃, be 1-6 hour drying time; Sintering temperature is 120～400 ℃, and roasting time is 2-8 hour.
7. according to the preparation method of the refining olefinic hydrocarbon expelling catalyzer of the described reformate of claim 6, it is characterized in that preferred baking temperature is 100-120 ℃, be 2-4 hour drying time; Preferred sintering temperature is 150～200 ℃, and roasting time is 3-4 hour.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006282658A (en) * | 2005-03-10 | 2006-10-19 | Mitsubishi Gas Chem Co Inc | Method for producing carboxylic acid or carboxylic acid ester |
| CN101116812A (en) * | 2007-07-30 | 2008-02-06 | 蒋玉珊 | Olefinic hydrocarbon expelling catalyzer and method for preparing the same |
| CN101502787A (en) * | 2009-02-09 | 2009-08-12 | 朱永林 | Method for preparing high-intensity water-resistant multifunctional high-efficient granule active clay preparation and use thereof |
-
2013
- 2013-05-13 CN CN2013101762741A patent/CN103230788A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006282658A (en) * | 2005-03-10 | 2006-10-19 | Mitsubishi Gas Chem Co Inc | Method for producing carboxylic acid or carboxylic acid ester |
| CN101116812A (en) * | 2007-07-30 | 2008-02-06 | 蒋玉珊 | Olefinic hydrocarbon expelling catalyzer and method for preparing the same |
| CN101502787A (en) * | 2009-02-09 | 2009-08-12 | 朱永林 | Method for preparing high-intensity water-resistant multifunctional high-efficient granule active clay preparation and use thereof |
Non-Patent Citations (1)
| Title |
|---|
| 何雅仙等: ""精制芳烃用颗粒白土的研制"", 《精细石油化工进展》, vol. 2, no. 6, 30 June 2001 (2001-06-30) * |
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Application publication date: 20130807 |