CN105195239A - Demetallized regeneration method for reformed aromatic refining catalyst - Google Patents

Abstract

The invention relates to a demetallized regeneration method for a reformed aromatic refining catalyst. The method comprises the following steps: (1) roasting an inactivated refining catalyst at a low temperature of 200 to 400 DEG C for 2 to 6 hours; (2) adding an appropriate amount of deionized water into the catalyst roasted at low temperature, wherein a mass ratio of the addition amount of the deionized water to the dry base of the catalyst is (3 to 20): 1, and stirring at a low speed till the catalyst is suspended; (3) adding an appropriate amount of organic acid to the solution in the step (2), wherein the organic acid is one or more of formic acid, acetic acid, oxalic acid and citric acid, a mass ratio of the organic acid to water is 1: (10 to 1000), stirring and heating to 50 to 100 DEG C, treating for 1 to 6 hours, discharging and washing; (4) drying the washed catalyst, and roasting at 300 to 600 DEG C for 2 to 8 hours. According to the method disclosed by the invention, the service life of the reformed aromatic refining catalyst is remarkably prolonged.

Description

A kind of demetalization renovation process of reformed arene catalyst for refining

Technical field

The present invention relates to aromatic hydrocarbons chemical field, specifically a kind of renovation process of reformed arene catalyst for refining, more particularly, the present invention relates to a kind of demetalization renovation process for reformed arene catalyst for refining inactivation.

Technical background

Reformed arene generally containing a small amount of alkene, must be removed: one is the decline that alkene may cause product quality, as: affect colourity, purity etc.; Two is that alkene can reduce the adsorbent of the device such as adsorbing separation, toluene disproportionation or the service life of catalyst.Industrial early stage Application comparison is adopt hydrofinishing and granular carclazyte technique non-hydrogenation two kinds of methods to remove widely.

Current non-hydrogenation process industry uses gradually novel molecular sieve class catalyst for refining substitute particles carclazyte, its single pass life can reach 6 ~ 10 times of carclazyte, and the de-alkene degree of depth is better than granular carclazyte, decreases poisonous useless solid discharge simultaneously.

In de-alkene subtractive process, the metal in feedstock oil such as Fe, Ni etc. deposit on a catalyst gradually, and along with the increase of amount of metal on catalyst, catalyst activity reduction, the generation of carbon distribution simultaneously causes the blocking in duct, and catalyst is inactivation gradually.

Can regenerate, after regeneration, how performance is related to operating cost and the use value of molecular sieve catalyst, but the current also imperfection of the regeneration techniques of such catalyst, bibliographical information is less, after most catalyst regeneration, hydraulic performance decline is serious, only has similar molecular sieve catalyst to have partial regeneration technology to report.

In existing deactivated molecular sieve catalyst Recycling Patents, a part stresses to consider how to prevent decaying catalyst from concentrating in regenerative process or the problem of excessive exotherms, as USP4202865 suggestion interval notes oxygen, USP4780195 then thinks add a certain amount of water to prevent sintering of catalyst in atmosphere.

A part of patent is then consider to carry out carbon deposit cleaning before catalyst roasting in addition, and patent CN100496746 discloses a kind of carbon deposit cleaner and the application in decaying catalyst regenerative process, then roasting regeneration.

Also have partial monopoly to remove light carbon distribution by in-situ regeneration, rinse as the catalyst nitrogen, steam etc. of inactivation are purged the mixed solutions such as rear peroxide, alcohol by patent CN102151589A, the method finally purged through steam, nitrogen etc. again regenerates.

Removing for metal, only have similar at high temperature use catalytic cracking catalyst regeneration have involved by, as:

CN1198366A proposes to remove toxic metals in Resid Fcc Catalyst by the method for hydrogen sulfide sulfuration, Oxidation of Carbon Monoxide and regenerates catalyst, thus makes renewing catalyst activity.

CN101219396A proposes and by acid treatment, skeleton structure is reconstructed, flourishing micropore-mesopore compound duct structural system is built in restructuring procedure, remove or heavy metal in passivation catalytic cracking spent catalyst, heavy metal removing rate reaches 30%, micro-activity improves more than 10 points, and shows the selective and lower coking yield of higher liquefied gas and gasoline.

CN1552804A proposes and at high temperature adopts acid, ammonium and activator to process catalytic cracking catalyst, significantly removes metallic pollution, improves catalyst performance.

CN101112694A proposes the metal that the method adopting hydrogen reducing, pickling, washing to combine removes catalytic cracking catalyst.

CN101116832A proposes the metal that the method adopting solid sulfur sulfuration, pickling and washing to combine removes catalytic cracking catalyst.

Correlative study shows, its deactivation cause of reformed arene finishing agent is mainly carbon distribution and metal deposition, and carbon distribution causes catalyst duct to block, de-rare ability declines and metal deposition easily causes carbon distribution in reaction generate thus cause rapid catalyst deactivation.At present, reformed arene finishing agent regeneration research is also only limitted to carbon distribution and removes, and there is no the research of report metal removal, the service life of regenerated catalyst is limited.

Summary of the invention

The object of the invention is to overcome the deficiencies in the prior art, a kind of demetalization renovation process of reformed arene catalyst for refining is provided, to improve the service life of generative reforming aromatic hydrocarbon refining catalyst further.

The present invention is a kind of demetalization renovation process of reformed arene catalyst for refining, and the method comprises the following steps:

(1) by inactivation catalyst for refining low-temperature bake, sintering temperature is 200 ~ 400 DEG C, and roasting time is 2 ~ 6 hours;

(2) add appropriate amount of deionized water by the catalyst after above-mentioned low-temperature bake, deionized water addition and catalyst butt mass ratio are 3 ~ 20:1, and stirring at low speed suspends to catalyst;

(3) appropriate organic acid is added in solution step (2) obtained, organic acid is formic acid, acetic acid, oxalic acid, citric acid wherein one or more, organic acid and water quality ratio are 1:10 ~ 1000, stirring is warming up to 50 ~ 100 DEG C, in 1 ~ 6 hour processing time, draw off, wash;

(4) by the product oven dry after above-mentioned washing, roasting, wherein sintering temperature is 300 ~ 600 DEG C, and roasting time is 2 ~ 8 hours.

According to demetalization renovation process of the present invention, its preferred version is characterised in that processing step comprises:

(1) by inactivation catalyst for refining low-temperature bake, sintering temperature is 300 ~ 350 DEG C, and roasting time is 2 ~ 3 hours;

(2) add appropriate amount of deionized water by the catalyst after above-mentioned low-temperature bake, deionized water addition and catalyst butt mass ratio are 5 ~ 8:1, and stirring at low speed suspends to catalyst;

(3) appropriate organic acid is added by above-mentioned solution, organic acid is formic acid, acetic acid, oxalic acid, citric acid wherein one or more, and organic acid and water quality ratio are 1:50 ~ 200, stirs and is warming up to 70 ~ 90 DEG C, in 2 ~ 4 hours processing times, draw off, wash;

(4) by the product oven dry after above-mentioned washing, roasting, sintering temperature is 500 ~ 550 DEG C, and roasting time is 3 ~ 5 hours.

The demetalization renovation process of reformed arene catalyst for refining of the present invention, compared with prior art, the inventive method significantly improves the service life of generative reforming aromatic hydrocarbon refining catalyst.

Detailed description of the invention

Below by way of comparative example and embodiment, the present invention is further described, but content not thereby limiting the invention.

In comparative example and embodiment, adopt reformation Fractionator Bottom oil as handling object.

Comparative example 1

Catalyst for refining TCDTO-1 (CNOOC Tianjin Chemical Research & Design Institute provides), note D1.

Comparative example 2

Inactivation TCDTO-1 catalyst for refining (CNOOC Tianjin Chemical Research & Design Institute provides), note D2.

Comparative example 3

The direct coke burning regeneration catalyst of inactivation catalyst for refining TCDTO-1, note D3.

Embodiment 1

Get 200gD2 and after roasting 3h, add in 1200ml deionized water at 300 DEG C, open be stirred to catalyst suspend, in above-mentioned suspension, add 4.8g acetic acid, be warming up to 80 DEG C process 3h, draw off, wash after at 500 DEG C roasting 4h namely obtain Samples EXAMPLE S1.

Embodiment 2

Get 200gD2 and after roasting 3h, add in 1200ml deionized water at 300 DEG C, open be stirred to catalyst suspend, in above-mentioned suspension, add 8g acetic acid, be warming up to 80 DEG C process 3h, draw off, wash after at 500 DEG C roasting 4h namely obtain embodiment S2.

Embodiment 3

Get 200gD2 and after roasting 3h, add in 1200ml deionized water at 300 DEG C, open be stirred to catalyst suspend, in above-mentioned suspension, add 16g acetic acid, be warming up to 80 DEG C process 3h, draw off, wash after at 500 DEG C roasting 4h namely obtain embodiment S3.

Embodiment 4

Get 200gD2 and after roasting 3h, add in 1200ml deionized water at 300 DEG C, open be stirred to catalyst suspend, in above-mentioned suspension, add 40g acetic acid, be warming up to 80 DEG C process 3h, draw off, wash after at 500 DEG C roasting 4h namely obtain embodiment S4.

Embodiment 5

Get 200gD2 and after roasting 3h, add in 1200ml deionized water at 200 DEG C, open be stirred to catalyst suspend, in above-mentioned suspension, add 16g acetic acid, be warming up to 80 DEG C process 3h, draw off, wash after at 500 DEG C roasting 4h namely obtain embodiment S5.

Embodiment 6

Get 200gD2 and after roasting 3h, add in 1200ml deionized water at 300 DEG C, open be stirred to catalyst suspend, in above-mentioned suspension, add 16g acetic acid, be warming up to 50 DEG C process 3h, draw off, wash after at 500 DEG C roasting 4h namely obtain embodiment S6.

Physical property characterizes

Carry out physical property sign to comparative example and embodiment sample, its result is as table 1:

Table 1 comparative example and embodiment sample physical data

Application examples

Carry out de-alkene ability to comparative example and embodiment to investigate, reaction condition is as follows: feedstock oil is oil at the bottom of reformation deheptanizer, and bromine index is 1086.5mgBr/100g; Reaction temperature 170 DEG C, reaction pressure 1.2MPa, weight space velocity 10h ^-1.

Table 2 different catalysts removes alkene ability (mgBr/100g)

Claims (2)

1. a demetalization renovation process for reformed arene catalyst for refining, is characterized in that comprising the following steps:

1) by inactivation catalyst for refining low-temperature bake, sintering temperature is 200 ~ 400 DEG C, and roasting time is 2 ~ 6 hours;

2) add appropriate amount of deionized water by the catalyst after above-mentioned low-temperature bake, deionized water addition and catalyst butt mass ratio are 3 ~ 20:1, and stirring at low speed suspends to catalyst;

3) by step 2) add appropriate organic acid in the solution that obtains, organic acid is formic acid, acetic acid, oxalic acid, citric acid wherein one or more, and organic acid and water quality ratio are 1:10 ~ 1000, stirs and is warming up to 50 ~ 100 DEG C, in 1 ~ 6 hour processing time, draw off, wash;

4) by obtained after the product oven dry after above-mentioned washing, roasting, wherein sintering temperature is 300 ~ 600 DEG C, and roasting time is 2 ~ 8 hours.

2., according to demetalization renovation process according to claim 1, it is characterized in that comprising the following steps:

1) by inactivation catalyst for refining low-temperature bake, sintering temperature is 300 ~ 350 DEG C, and roasting time is 2 ~ 3 hours;

2) add appropriate amount of deionized water by the catalyst after above-mentioned low-temperature bake, deionized water addition and catalyst butt mass ratio are 5 ~ 8:1, and stirring at low speed suspends to catalyst;

3) by step 2) add appropriate organic acid in the solution that obtains, organic acid is formic acid, acetic acid, oxalic acid, citric acid wherein one or more, and organic acid and water quality ratio are 1:50 ~ 200, stirs and is warming up to 70 ~ 90 DEG C, in 2 ~ 4 hours processing times, draw off, wash;

4) by obtained after the product oven dry after above-mentioned washing, roasting, wherein sintering temperature is 500 ~ 550 DEG C, and roasting time is 3 ~ 5 hours.