CN1065902C - Process for removing sulfuric acid radial from reforming catalyst - Google Patents
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- CN1065902C CN1065902C CN98117895A CN98117895A CN1065902C CN 1065902 C CN1065902 C CN 1065902C CN 98117895 A CN98117895 A CN 98117895A CN 98117895 A CN98117895 A CN 98117895A CN 1065902 C CN1065902 C CN 1065902C
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- catalyst
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- organochlorine compound
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Abstract
The present invention relates to a method for removing sulfuric acid radials from a reforming catalyst. At a temperature of 400 to 600 DEG C, hydrogen gas is introduced into a catalyst bed layer to decompose organochlorine compounds of hydrogen chloride; the introduced quantity of the organochlorine compound is 0.2 to 8.0% of the weight of the catalyst measured by chlorine elements, and the organochlorine compound is selected from dichloroethane or carbon tetrachloride. The method of the present invention is suitable for the regeneration of reforming catalysts contaminated by sulfuric acid radicals to restore the catalyst activity.
Description
The present invention relates to a kind of renovation process of reforming catalyst, specifically, is the removal methods of sulfate radical on a kind of reforming catalyst.
Behind the reforming catalyst inactivation, conventional renovation process is to make charcoal by control regeneration gas oxygen level and temperature, and then carry out that chlorination is upgraded and reduction is handled, it is to feed a certain amount of organochlorine compound under the high temperature oxygen-containing atmosphere in catalyzer that said chlorination is upgraded, at high temperature make the abundant oxidation of metal, so that accumulative platinum crystal grain redispersion, and the chlorine component of replenish loss, to improve the performance of catalyzer.This method is applicable to the regenerative process because of the catalyzer of normal carbon deposit inactivation.
In catforming process, sulphur is the common factor that causes poisoning of catalyst, though in the fixed bed reformer, sulphur content in the catalytic reforming feedstock is strictly controlled, but some abnormal factorses, reduce as the upstream catalyst for pre-hydrogenation is active, leak in the pre-hydrogenation input and output material interchanger, dehydration by evaporation tower operation fluctuation etc. all can make reforming catalyst be subjected to the pollution of high-sulfur oils and reduce activity.The reason that causes the reforming catalyst sulfur poisoning has two kinds, a kind of is under during operation the reductive condition, hydrogen sulfide is attracted to the metal active center and makes catalyst activity reduction, another kind is in catalyst regeneration is made charcoal process, sulfide (Iron sulfuret and other sulfide) is oxidized, forms sulfate radical and make poisoning of catalyst on support of the catalyst.
Poisoning for first kind of form, renovation process is hot hydrogen desulfurization, that is: cut-out charging, under comparatively high temps, for example use hydrogen recycle for 500～510 ℃, make the sulphur that is adsorbed on the catalyst metal active centre generate the hydrogen sulfide desorption and transfer in the circulation gas, remove hydrogen sulfide in the circulation gas with the method for displacement, alkali cleaning or molecular sieve adsorption again.
Poisoning for second kind of form, hot hydrogen treatment process with routine is difficult to remove sulfate radical, and the existence of sulfate radical not only makes the aromatization activity selectivity of catalyzer obviously reduce, also make cl content decline in the catalyzer, and make chlorination renewal benefit chlorine difficulty in the catalyst regeneration process.
For avoiding in the reforming catalyst regenerative process by sulfate pollution, USP4482637 proposes that controlled temperature is 399～427 ℃ in burning process, burns back controlled oxidation temperature and can make the sulphur on device and the catalyzer be transformed into SO2 and seldom generate SO for 399～427 ℃
3Thereby, reduce SO
4 2-Formation.But this method can not remove already present SO on the catalyzer
4 2-
The removal methods that the purpose of this invention is to provide sulfate radical on a kind of reforming catalyst, this method can make by the reforming catalyst of sulfate pollution recovers active.
The inventive method is to fed hydrogen and the organochlorine compound that can decomposite hydrogenchloride under this condition by the reforming catalyst bed of sulfate pollution at 400～600 ℃, the feeding amount of organochlorine compound is counted 0.2～8.0% of catalyst quality with elemental chlorine, and makes the hydrogenchloride that decomposites penetrate beds.
Described organochlorine compound is a chloroparaffin, the number of chlorine atom can be 1～4 in the chloroparaffin, as an alkyl chloride, dichloro-alkane, three alkyl chloride or four alkyl chloride, preferred carbonatoms is 1～6 a chloroparaffin, and most preferred chloroparaffin is ethylene dichloride, trichloroethane or tetracol phenixin.
The temperature that removes sulfate radical in the inventive method should be controlled at 400～600 ℃, and temperature is too low, is lower than 400 ℃, and sulfate radical is difficult for by H
2Be reduced into H
2S; Temperature is too high, surpasses 600 ℃, can cause catalyzer platinum crystal grain coalescent.
The hydrogen that feeds in the described method and the volume ratio of catalyzer are 200～4000: 1 hour
-1, be preferably 700～2000: 1 hour
-1
In the inventive method, the hydrogen that feeds to the reforming catalyst bed can be one-pass, also the hydrogen gas recycle that feeds can be used.For the one-pass device of hydrogen, the amount that feeds organochlorine compound is counted 1.0～8.0% of catalyst quality with chlorine, is preferably 2.0～4.0%; The time that feeds organochlorine compound is preferably 1.0～5.0 hours.For the device of hydrogen recycle, the amount that fed organochlorine compound in 1.0～5.0 hours is preferably 0.2～2.0% of catalyst quality in chlorine.
In the methods of the invention, in hot hydrogen stream, feed organochlorine compound, can make sulfate radical reduction the becoming H in the catalyzer
2S and desorption, thus make the reforming catalyst of poisoning recover active because of sulfate radical.After stopping to feed organochlorine compound, preferably continue to feed hydrogen or adopt other method with the H that produces
2S is with from beds, and makes the H of outflow catalyst bed
2S content is less than 1ppm, to reach in the reforming process process requirement to sulphur content.
The inventive method is applicable to by the regeneration of the reforming catalyst of sulfate pollution.By the reforming catalyst of sulfate pollution, can make it recover active for merely with the inventive method.For the catalyzer of inactivation in the industrial operation process, can before regenerative process, use the inventive method and remove sulfate radical, after also can burning in regenerative process, before chlorination was upgraded, application the inventive method removed the sulfate radical on the catalyzer.
The inventive method makes that the sulfate radical on the reforming catalyst is reduced generation H owing to feed an amount of organochlorine compound in hot hydrogen stream
2S and desorption, thus reach the purpose that removes sulfate radical, make catalyzer recover active.By the reforming catalyst of sulfate pollution, can make the level of its activation recovering for merely to suitable live catalyst with the inventive method.For the reforming catalyst of inactivation,, wherein also comprise sulfate radical owing to the reason that causes its inactivation is many-sided by industrial operation, therefore, after removing sulfate radical with the inventive method, carry out chlorination with conventional method again and upgrade, catalyst performance will be recovered better.
Further describe the present invention below by embodiment, but the present invention is not limited to this.
Example 1～3
Following example removes sulfate radical with the inventive method, makes catalyst regeneration recover active.
To contain the heavy % of Pt0.30, the heavy % of Re0.27, SO
4 2-0.28 the reforming catalyst that poison in the running back on full scale plant 100 grams of heavy %, put into quartz tube reactor, feed hydrogen and a certain amount of ethylene dichloride (Beijing Chemical Plant's production) under 510 ℃ of normal pressures, wherein the volume ratio of hydrogen and catalyzer is 500: 1 hours
-1After feeding the ethylene dichloride certain hour, change logical pure hydrogen gas and obtain catalyst A～C after for some time, it removes SO
4 2-The results are shown in table 1.Wherein adopt colorimetric method to measure SO
4 2-Content.
Comparative Examples 1
This example is investigated conventional renovation process and is removed SO
4 2-Effect.
Get the indusqtrial poisoning catalyzer identical with example 1 100 grams, regenerate with the chlorination updating method of routine, promptly normal pressure, 500 ℃, the volume ratio of air and catalyzer is 700: 1 hours
-1Condition under, fed ethylene dichloride 2 hours with the cl content that per hour accounts for catalyst quality 2.0%, continue activation 4 hours again, then at normal pressure, 480 ℃, hydrogen/catalyst volume than=500: 1 hour
-1Condition under the reduction 4 hours, obtain regenerated catalyst D.SO among the catalyzer D
4 2-Content is 0.27 heavy %, and its value is listed in table 1.
Comparative Examples 2
This Comparative Examples is investigated and is removed SO in the reforming catalyst with hot hydrogen stream
4 2-Effect.
Get the indusqtrial poisoning catalyzer identical 100 grams, under 510 ℃, with 500: 1 hours with example 1
-1Gas agent volume ratio feed hydrogen and obtained catalyzer E in 24 hours, the sulfate radical content among the catalyzer E is 0.22 heavy %, its value is listed in table 1.
By table 1 data as can be known, can remove SO in the indusqtrial poisoning catalyzer substantially with the inventive method
4 2-, and handle with the conventional regeneration method or with hot hydrogen, then can not remove the SO in the indusqtrial poisoning catalyzer basically
4 2-
Example 4
This example takes off SO with the inventive method to the reforming catalyst that the bright sulfur acid group pollutes
4 2-Handle, and investigate its catalytic effect.
Get the fresh reforming catalyst that 80 grams contain the heavy % of Pt0.21 heavy %, Re0.42 and put into fixed-bed reactor, the air 2 hours that contains small amounts of sulfur dioxide 500 ℃ of feedings, make this catalyst surface form sulfate radical and poison, the content of sulfate radical is 1.2 heavy % in the catalyzer, and this is removed SO because of the sulfate radical fouled catalyst with the method for example 3
4 2-, remove SO
4 2-The content of sulfate radical is 0.06 heavy % in the rear catalyst.
With live catalyst, because of SO
4 2-And poisoned catalyst and take off SO
4 2-After catalyzer carry out micro anti-evaluation experiment respectively.Estimating procatalyst all handles through prevulcanized.Estimating raw materials used is normal heptane, and evaluation temperature is 500 ℃, and pressure is that 0.98MPa, feed volume air speed are 6.0 hours
-1, hydrogen to oil volume ratio is 1200: 1, evaluation result sees Table 2.
As shown in Table 2, the SO on the reforming catalyst
4 2-Its activity is reduced greatly, and with behind the inventive method processing catalyzer, its aromatization activity recover fully.
Example 5
This example explanation the inventive method is to the influence of industrial operation poisoned catalyst regenerability.
Get the indusqtrial poisoning catalyzer identical 100 grams, put into quartz tube reactor, take off SO by the method for example 3 with example 1
4 2-After the processing, regenerate according to the ordinary method of Comparative Examples 1 again, make regenerated catalyst C '.
After the prevulcanized of catalyzer C ' process, be raw material, 500 ℃, 1.0MPa, feed volume air speed 6.0 hours with the normal heptane
-1, under 1200: 1 the condition of hydrogen to oil volume ratio catalyzer C ' being carried out the aromatization activity evaluation, it the results are shown in Table 3.
Comparative Examples 3
With example 1 described indusqtrial poisoning catalyzer, carry out hot hydrogen by the method for Comparative Examples 2 and handle, with the ordinary method regeneration of Comparative Examples 1, make regenerated catalyst E ' then.With normal heptane is raw material, carries out the aromatization activity evaluation experimental by the method for example 5, the results are shown in Table 3.
Because commercial catalysts poisoning factor is a lot, only can remove sulfate radical with the inventive method, its activity is restored, but as can be known by table 3 data, after removing sulfate radical with the inventive method, the catalyzer of regenerating and obtaining with ordinary method is handled the catalyzer aromatization activity height that obtains with ordinary method regeneration again than simple with ordinary method regeneration or with hot hydrogen again, and its numerical value is substantially near the live catalyst level.
Table 1
Table 2
| SO in the catalyzer 4 2-Content, heavy % | Product is formed, heavy % | ||||
| C 1～C 2 | C 1～C 5 | Benzene+toluene | Transformation efficiency | ||
| Live catalyst | 0 | 4．49 | 35．21 | 25．46 | 91．62 |
| Because of SO 4 2-Fouled catalyst | 1．2 | 3．24 | 24．19 | 11．24 | 73．98 |
| Take off SO 4 2-After catalyzer | 0．06 | 3．50 | 32．76 | 25．62 | 88．32 |
Table 3
| SO in the catalyzer 4 2-Content, heavy % | Product is formed, heavy % | ||||
| C 1～C 2 | C 1～C 5 | Benzene+toluene | Transformation efficiency | ||
| Live catalyst | 0 | 8．58 | 51．61 | 28．40 | 96．06 |
| C＇ | 0．06 | 9．46 | 48．89 | 27．68 | 94．35 |
| E＇ | 0．23 | 8．83 | 49．07 | 24．96 | 94．16 |
| D | 0．27 | 8．95 | 53．40 | 24．93 | 94．83 |
Claims (5)
1, the removal methods of sulfate radical on a kind of reforming catalyst, be to feed hydrogen and the organochlorine compound that can under this condition, decomposite hydrogenchloride to beds at 400～600 ℃, per hour the feeding amount of hydrogen is 200～4000 times of catalyst volume, the feeding amount of organochlorine compound is counted 0.2～8.0% of catalyst quality with elemental chlorine, and making the hydrogenchloride that decomposites penetrate beds, described organochlorine compound is ethylene dichloride, trichloroethane or tetracol phenixin.
2, in accordance with the method for claim 1, it is characterized in that described hydrogen is once to pass through beds, the feeding amount of organochlorine compound is counted 1.0～8.0% of catalyst quality with chlorine.
3, in accordance with the method for claim 1, it is characterized in that described hydrogen cycles through beds, the feeding amount of organochlorine compound is counted 0.2～2.0% of catalyst quality with chlorine.
4, according to claim 2 or 3 described methods, the time that it is characterized in that feeding organochlorine compound is 1.0～5.0 hours.
5, in accordance with the method for claim 1, after it is characterized in that stopping to feed organochlorine compound, continue to feed the H that hydrogen makes the outflow catalyst bed
2S concentration is less than 1ppm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98117895A CN1065902C (en) | 1998-09-03 | 1998-09-03 | Process for removing sulfuric acid radial from reforming catalyst |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98117895A CN1065902C (en) | 1998-09-03 | 1998-09-03 | Process for removing sulfuric acid radial from reforming catalyst |
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| CN1246517A CN1246517A (en) | 2000-03-08 |
| CN1065902C true CN1065902C (en) | 2001-05-16 |
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101153227B (en) * | 2006-09-29 | 2010-09-22 | 中国石油化工股份有限公司 | Continuous reforming catalyst desulfurizing method |
| CN102166534A (en) * | 2010-02-26 | 2011-08-31 | 中国石油化工股份有限公司 | Method for removing sulfate radicals from continuous reforming catalyst |
| CN105363446B (en) | 2014-08-25 | 2019-06-14 | 中国石油化工股份有限公司 | A kind of catalyst for reforming naphtha and preparation method |
| CN106140326B (en) * | 2015-03-25 | 2019-08-16 | 中国石油化工股份有限公司 | The regeneration method of semi regeneration reforming catalyst |
| TWI681816B (en) | 2015-03-25 | 2020-01-11 | 中國石油化工科技開發有限公司 | Regeneration method of semi-regeneration recombination catalyst |
| CN112316987A (en) * | 2019-08-05 | 2021-02-05 | 中国石油化工股份有限公司 | Desulfurization method of carbon deposition low-carbon alkane dehydrogenation catalyst |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4482637A (en) * | 1982-08-04 | 1984-11-13 | Chevron Research Company | In situ hydrocarbon conversion catalyst regeneration and sulfur decontamination of vessels communicating with catalyst reactor |
| CN1093951A (en) * | 1992-12-08 | 1994-10-26 | 恩格尔哈德公司 | The composition and method of making the same that is used for the catalytic cracking passivating vanadium |
-
1998
- 1998-09-03 CN CN98117895A patent/CN1065902C/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4482637A (en) * | 1982-08-04 | 1984-11-13 | Chevron Research Company | In situ hydrocarbon conversion catalyst regeneration and sulfur decontamination of vessels communicating with catalyst reactor |
| CN1093951A (en) * | 1992-12-08 | 1994-10-26 | 恩格尔哈德公司 | The composition and method of making the same that is used for the catalytic cracking passivating vanadium |
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