CN106345499A - Preparation method of attapulgite catalyst of load phosphorus element and application thereof in reforming and generating oil-removed trace olefin - Google Patents
Preparation method of attapulgite catalyst of load phosphorus element and application thereof in reforming and generating oil-removed trace olefin Download PDFInfo
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- CN106345499A CN106345499A CN201610631703.3A CN201610631703A CN106345499A CN 106345499 A CN106345499 A CN 106345499A CN 201610631703 A CN201610631703 A CN 201610631703A CN 106345499 A CN106345499 A CN 106345499A
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- attapulgite
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/182—Phosphorus; Compounds thereof with silicon
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G29/00—Refining of hydrocarbon oils, in the absence of hydrogen, with other chemicals
- C10G29/02—Non-metals
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/70—Catalyst aspects
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- Chemical Kinetics & Catalysis (AREA)
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- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention discloses a preparation method of attapulgite catalyst of load phosphorus element and application of attapulgite catalyst in reforming and generating oil-removed trace olefin. The preparation method comprises steps of acidizing attapulgite by inorganic acid, obtaining attapulgite acidized by inorganic acid, and performing suction filtration and drying; steeping the dried acidized attapulgite by phosphoric acid with certain concentration to perform modified treatment; adding the molding assistant to the modified attapulgite, and then shaping, drying, and roasting; finally, obtaining the catalyst. The catalyst prepared by the invention has the advantages of replacing the existed attapulgite catalyst under the condition of not changing an acidized attapulgite deolefination device, and removing trace olefin reformed and generated to be oil; the catalyst is simple in preparation technique, low in cost, short in reaction time, and high in percent conversion; the catalyst life is more than 10 months, and is 2-3 months more than the service life of the acidized attapulgite.
Description
Technical field
The invention belongs to Speciality Petrochemicals field is and in particular to a kind of system of the Attapulgite Catalyst of load P elements
Preparation Method and its application in reforming and generating oil-off eliminating minute alkene.
Background technology
A certain amount of olefin impurity, these olefin impurity properties are contained in reformed oil (intermediate products of aromatics production)
Enliven very much it is easy to polymerization forms colloid affects the quality of aromatic hydrocarbon product, even if olefin(e) centent considerably less (ppm level) also can be right
Subsequent reactions process produces very detrimental effect.In order to obtain qualified industrial chemicals and ensure smoothly entering of subsequent technique
Row it is necessary to by olefin removal a small amount of in reformed oil, to improve the economic benefit of aromatic hydrocarbons processing technique.
Reforming and generating oil-off olefin technique has following 4 kinds:Clay-filtered；Hydrogenation catalyst refines；Molecular sieve catalytic
Refined；Group technology refines.Wherein methodWithIt is maturation process, be industrially applied, methodWithIt is currently to develop focus.
He Yaxian etc., the development [j] of refined aromatic hydrocarbons granular carclazyte. Speciality Petrochemicals is in progress, and 2001,2 (6): 15-
22, using x x ray diffraction, pore-size distribution test and deolefination evaluation test, determine the hargil mineral resources of high-quality, have studied acidifying
The impact to granular carclazyte performance of condition, binding agent and sintering temperature, is prepared for the granular carclazyte of high-quality.
Wang Ming etc., Industrial Evaluation of Particulate Clay for Aromatic Refining [j]. fine-chemical intermediate, 2004,34 (4): 66-72,
By industrial side line evaluation test, under the conditions of device technique, to effect in the process of reformation oil-off olefin for 4 kinds of Emathlites
Evaluated, and made technical economic analysis.
But the life-span of granular carclazyte is comparatively short, typically it is about 2-3 month, catalyst loading and unloading intensity is high, and ambient pressure is big.
Therefore, develop a kind of life-span length and the catalyst of environmental protection is significant.
Content of the invention
For the deficiencies in the prior art, the invention provides a kind of preparation side of the Attapulgite Catalyst of load P elements
Method and its application in reforming and generating oil-off eliminating minute olefine reaction.
The present invention is achieved by the following technical solutions:
A kind of preparation method of the Attapulgite Catalyst of load P elements, comprises the steps:
Step one, carries out acidification with inorganic acid solution to attapulgite, obtains mineral acid acidified attapulgite, filter,
Dry；
Step 2, the acidifying attapulgite being obtained with phosphoric acid solution impregnation steps one is modified processing；
Step 3, the modified attapulgite that step 2 is obtained adds shaping assistant aftershaping, drying, roasting to obtain final product load
The Attapulgite Catalyst of P elements；
Wherein, described mineral acid is sulphuric acid or hydrochloric acid；Described shaping assistant is sesbania powder.
Inorganic acid solution concentration described in step one is 0.5mol/l～2 mol/l；The concentration 0.1 of phosphoric acid solution described in step 2
mol/l ~2 mol/l.
The mass ratio of attapulgite described in step one and inorganic acid solution is 1:3～6；It is acidified attapulgite described in step 2
Mass ratio with phosphoric acid solution is 1:3～6.
Described in step 2, dipping heating-up temperature is 50 DEG C～90 DEG C, time 6～24h.
Drying temperature described in step 3 is 100 DEG C～120 DEG C, and sintering temperature is 300 DEG C～550 DEG C, and the time is 3～5h.
The further improvement project of the present invention is:
The catalyst that above-mentioned preparation method is obtained is used for removing trace amounts of olefin for reformed oil.
The present invention further improvement project is:
The catalyst that above-mentioned preparation method is obtained is used for the method that reformed oil is used for removing trace amounts of olefin.
The invention has the benefit that
The catalyst long service life of the present invention.Carry out the examination of reforming and generating oil-off eliminating minute alkene life-span with catalyst of the present invention
Test, be 3 mpa, volume space velocity 2h keeping pressure-1In the case of constant, control 180 DEG C of initial reaction temperature, if sample tap produces
The bromine index of product is more than or equal to 100mgbr/100g oil, then improve 10 DEG C of temperature, until reaction temperature rises to 230 DEG C and is
Only, judge that the life-span is investigated to terminate, the life-span average out to of catalyst more than 300 days, the 2-3 being far longer than the catalyst of only acidifying is individual
Month.
The catalyst of the present invention is used in reforming and generating oil-off eliminating minute alkene, improves the removal efficiency of alkene, to reform
Generate the bromine index meter in oil, two fixed beds under the same conditions can to this catalyst of experiment and acidifying Attapulgite Catalyst
To obtain, the optimal bromine index of this catalyst is 26mgbr/100g oil, and its conversion ratio is 99.32%, and is acidified attapulgite
Good oily for 298mgbr/100g, its conversion ratio is 92.31%.
This catalyst does not need using assistant products such as template, so the waste material producing is few, and in experimentation, no
Toxic and harmful can be produced, only produce a small amount of ammonia, atom utilization is high, meets Green Chemistry standard.
Specific embodiment
Embodiment 1
Weigh in the beaker that 10 grams of attapulgites add the dilution heat of sulfuric acid being 0.5mol/l equipped with 40ml concentration, be heated to 90
DEG C, stir 2h, cooling is taken out, then take the attapulgite after acidifying to add the phosphoric acid solution for 0.5mol/l equipped with 40ml concentration
Beaker in, be heated to 70 DEG C, impregnate 12h, sucking filtration dry.After adding shaping assistant molding, dry 12h, 300 DEG C of roastings for 110 DEG C
Burn 4h, obtain catalyst.
Take the catalyst 5g preparing, load in fixed bed continuous tubular reactor, (raw material bromine index is reformed oil
3877mgbr/100g oil) to be squeezed in reactor with pump, holding pressure is 3mpa, controls 190 DEG C of temperature, air speed 4h-1, reactor
Outlet sample analysis bromine index is 86mgbr/100g oil, and its conversion ratio (initial activity) is 97.78%.
Embodiment 2
Weigh in the beaker that 10 grams of attapulgites add the dilution heat of sulfuric acid being 1mol/l equipped with 30ml concentration, be heated to 80 DEG C,
Stirring 1h, cooling is taken out, then takes the attapulgite after acidifying to add the burning of the phosphoric acid solution being 1mol/l equipped with 30ml concentration
In cup, it is heated to 70 DEG C, impregnates 16h, sucking filtration is dried.After adding shaping assistant molding, dry 12h, 550 DEG C of roasting 4h for 110 DEG C,
Obtain catalyst.
Take the catalyst 5g preparing, load in fixed bed continuous tubular reactor, (raw material bromine index is reformed oil
3877mgbr/100g oil) to be squeezed in reactor with pump, holding pressure is 3.5 mpa, controls 200 DEG C of temperature, air speed 2h-1, instead
Device outlet sample analysis bromine index is answered to be 46mgbr/100g oil, its conversion ratio (initial activity) is 98.81%.
Embodiment 3
Weigh in the beaker that 10 grams of attapulgites add the dilution heat of sulfuric acid being 2mol/l equipped with 60ml concentration, be heated to 70 DEG C,
Stirring 2h, cooling is taken out, then takes the attapulgite after acidifying to add the burning of the phosphoric acid solution being 2mol/l equipped with 60ml concentration
In cup, it is heated to 70 DEG C, impregnates 24h, sucking filtration is dried.After adding shaping assistant molding, dry 12h, 450 DEG C of roasting 3h for 110 DEG C,
Obtain catalyst.
Take the catalyst 5g preparing, load in fixed bed continuous tubular reactor, (raw material bromine index is reformed oil
3877mgbr/100g oil) to be squeezed in reactor with pump, holding pressure is 3 mpa, controls 220 DEG C of temperature, air speed 2h-1, reactor
Outlet sample analysis bromine index is 26mgbr/100g oil, and its conversion ratio (initial activity) is 99.32%.
Embodiment 4
Weigh in the beaker that 10 grams of attapulgites add the dilute hydrochloric acid solution being 2mol/l equipped with 50ml concentration, be heated to 80 DEG C,
Stirring 1h, cooling is taken out, then takes the attapulgite after acidifying to add the beaker of the phosphoric acid solution being 2mol/l equipped with 50ml concentration
In, it is heated to 80 DEG C, impregnates 24h, sucking filtration is dried.After adding shaping assistant molding, dry 12h, 350 DEG C of roasting 4h for 110 DEG C, obtain
To catalyst.
Take the catalyst 5g preparing, load in fixed bed continuous tubular reactor, (raw material bromine index is reformed oil
3877mgbr/100g oil) to be squeezed in reactor with pump, holding pressure is 3.5mpa, controls 230 DEG C of temperature, air speed 10h-1, instead
Device outlet sample analysis bromine index is answered to be 95mgbr/100g oil, its conversion ratio (initial activity) is 97.78%.
The life test of embodiment 5-
The catalyst 5g that Example 3 prepares, loads in fixed bed continuous tubular reactor, (raw material bromine refers to reformed oil
Number is 3877mgbr/100g oil) to be squeezed in reactor with pump, holding pressure is 3 mpa, air speed 2h-1In the case of constant, control
180 DEG C of initial reaction temperature, if the bromine index of sample tap product is more than or equal to 100mgbr/100g oil, improves 10 DEG C of temperature,
Until till reaction temperature rises to 230 DEG C, life-span investigation terminates.The life-span of embodiment 3 catalyst is 302 days, and result is shown in
Following table:
The catalyst that embodiment 1/2/4 is prepared, carries out life-span investigation using test method similarly to Example 5, averagely
Life-span is more than 300 days.
Claims (9)
1. a kind of preparation method of the Attapulgite Catalyst of load P elements is it is characterised in that comprise the steps:
Step one, carries out acidification with inorganic acid solution to attapulgite, obtains mineral acid acidified attapulgite, filter,
Dry；
Step 2, the acidifying attapulgite being obtained with phosphoric acid solution impregnation steps one is modified processing；
Step 3, the modified attapulgite that step 2 is obtained adds shaping assistant aftershaping, drying, roasting to obtain final product load
The Attapulgite Catalyst of P elements.
2. according to claim 1 a kind of load P elements Attapulgite Catalyst preparation method it is characterised in that:
Mineral acid described in step one is sulphuric acid or hydrochloric acid；Inorganic acid solution concentration is 0.5mol/l～2 mol/l.
3. the preparation method of the Attapulgite Catalyst of a kind of load P elements according to claim 1 and 2, its feature exists
In: the mass ratio of attapulgite described in step one and inorganic acid solution is 1:3～6.
4. according to claim 1 a kind of load P elements Attapulgite Catalyst preparation method it is characterised in that:
Concentration 0.1 mol/l ~ 2 mol/l of phosphoric acid solution described in step 2, acidifying attapulgite described in step 2 and phosphoric acid solution
Mass ratio is 1:3～6.
5. according to claim 1 a kind of load P elements Attapulgite Catalyst preparation method it is characterised in that:
Described shaping assistant is sesbania powder.
6. according to claim 1 a kind of load P elements Attapulgite Catalyst preparation method it is characterised in that:
Described in step 2, dipping heating-up temperature is 50 DEG C～90 DEG C, time 6～24h.
7. according to claim 1 a kind of load P elements Attapulgite Catalyst preparation method it is characterised in that:
Drying temperature described in step 3 is 100 DEG C～120 DEG C, and sintering temperature is 300 DEG C～550 DEG C, and the time is 3～5h.
8. the catalyst that arbitrary preparation method described in claim 1 to 7 is obtained is used for removing trace amounts of olefin for reformed oil.
9. the catalyst that arbitrary preparation method described in claim 1 to 7 is obtained is used for removing trace amounts of olefin for reformed oil
Method.
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| CN201610631703.3A CN106345499B (en) | 2016-08-04 | 2016-08-04 | It is a kind of load P elements Attapulgite Catalyst preparation method and its reformed oil removing trace amounts of olefin in application |
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| CN201610631703.3A CN106345499B (en) | 2016-08-04 | 2016-08-04 | It is a kind of load P elements Attapulgite Catalyst preparation method and its reformed oil removing trace amounts of olefin in application |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102728394A (en) * | 2011-04-13 | 2012-10-17 | 南京亚东奥土矿业有限公司 | Preparation method and application of acid modified attapulgite clay catalyst |
| CN103012035A (en) * | 2012-11-28 | 2013-04-03 | 浙江工业大学 | Method for removing trace hydrocarbon out of aromatic hydrocarbon by utilizing HMCM-41 type mesoporous molecular sieve |
| CN104588089A (en) * | 2015-01-07 | 2015-05-06 | 盱眙恒信粘土科技有限公司 | Reformate olefin-removal catalyst preparation method by ammonium fluoride modification |
| WO2015090084A1 (en) * | 2013-12-18 | 2015-06-25 | 西安近代化学研究所 | Catalyst for synthesizing ethylenimine as well as preparation method and application thereof |
| CN105536760A (en) * | 2015-12-03 | 2016-05-04 | 淮阴工学院 | Preparation method of composite clay alkene removal catalyst with high and lasting effect |
-
2016
- 2016-08-04 CN CN201610631703.3A patent/CN106345499B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102728394A (en) * | 2011-04-13 | 2012-10-17 | 南京亚东奥土矿业有限公司 | Preparation method and application of acid modified attapulgite clay catalyst |
| CN103012035A (en) * | 2012-11-28 | 2013-04-03 | 浙江工业大学 | Method for removing trace hydrocarbon out of aromatic hydrocarbon by utilizing HMCM-41 type mesoporous molecular sieve |
| WO2015090084A1 (en) * | 2013-12-18 | 2015-06-25 | 西安近代化学研究所 | Catalyst for synthesizing ethylenimine as well as preparation method and application thereof |
| CN104588089A (en) * | 2015-01-07 | 2015-05-06 | 盱眙恒信粘土科技有限公司 | Reformate olefin-removal catalyst preparation method by ammonium fluoride modification |
| CN105536760A (en) * | 2015-12-03 | 2016-05-04 | 淮阴工学院 | Preparation method of composite clay alkene removal catalyst with high and lasting effect |
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