CN106140326B - The regeneration method of semi regeneration reforming catalyst - Google Patents
The regeneration method of semi regeneration reforming catalyst Download PDFInfo
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- CN106140326B CN106140326B CN201510134342.7A CN201510134342A CN106140326B CN 106140326 B CN106140326 B CN 106140326B CN 201510134342 A CN201510134342 A CN 201510134342A CN 106140326 B CN106140326 B CN 106140326B
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Abstract
A kind of regeneration method of semi regeneration reforming catalyst, including sulfate radical is introduced after reclaimable catalyst is made charcoal thereto, then carry out chlorination update and reduction.Catalyst after method regeneration is not required to presulfurization, has better regeneration effect.
Description
Technical field
The present invention is a kind of regeneration method of catalyst for reforming naphtha, specifically, being a kind of naphtha semi regeneration weight
The regeneration method of whole catalyst.
Background technique
Catalytic reforming is with C6~C12Naphtha Cut be raw material, in certain temperature, pressure, face hydrogen and catalyst and exist
Under, make raw material hydrocarbon molecule that the reforming reactions such as cycloalkane dehydrogenation, linear alkanes dehydrogenation isomery, paraffin dehydrogenation cyclisation, production occur
High-knock rating gasoline blend component or aromatic hydrocarbons, and the process of the cheap hydrogen of by-product.It is widely used in catalytic reforming process at present
The heterogeneous acidic function that support type dual-function reforming catalyst, the hydrogenation/dehydrogenation function of providing including metal constituent element and carrier provide
Energy.Reforming catalyst be usually using activated alumina as carrier, Pt be main metal constituent element, and containing the second metal constituent element such as rhenium,
Bis- (more) metallic catalysts of tin or germanium.
For dual-function reforming catalyst, metal function and acid function are acted synergistically on certain matching degree and are catalyzed weight
Whole reaction.If metal hydrogenation/dehydrogenation activity function is too strong in the two, the carbon deposit on reforming catalyst surface can increase sharply, no
Conducive to continuing for reforming reaction, metal function is too weak, and catalyst activity reduces.If acid too strong, catalyst adds hydrogen to split
Change activity is stronger, and the liquid yield of reformate can reduce, and acid too weak, activity reduces.Therefore support acidity function and metal
The balance matching of function determines the activity, selectivity and stability of catalyst.
In addition, for platinum-rhenium catalyst used in semi-regenerating catalytic reforming, since rhenium metal has very high hydrogenolysis activity,
If not being passivated the activity of rhenium when going into operation, strong hydrogenolysis will occur at oil inlet initial stage, release a large amount of reaction heat, make to be catalyzed
Agent bed temperature increases rapidly, overheating problem occurs.Once there is this phenomenon, it often will cause serious consequence, gently then cause
The a large amount of carbon deposits of catalyst, damage the activity and stability of catalyst, heavy then burn out catalyst, reactor and inner member.Therefore
Platinum-rhenium reforming catalyst is needed before use by presulfurization, by presulfurization, the hydrogenolysis for inhibiting fresh catalyst excessive,
With the activity and stability of guard catalyst, improve the selectivity of catalyst.The method for carrying out presulfurization to platinum-rhenium catalyst has
Two kinds: one is H is introduced in hydrogen2S slowly carries out presulfurization to catalyst under certain temperature and pressure；It is another
Kind is that organic sulfur compound, such as dimethyl disulfide, dimethyl sulfide are injected in hydrogen under certain temperature, pressure, is used
The H that these organic sulfur compounds are formed after decomposing2S carries out presulfurization to catalyst.First method is generally used for laboratory research,
Second method is commonly used to going into operation for platinum-rhenium catalyst commercial plant.The essence of both methods is all to use H2S is to catalyst
Presulfurization is carried out, gas-phase presulfiding is belonged to.There are the environmental pollution of equipment burn into and safety are hidden for the presulfurization of platinum-rhenium reforming catalyst
The problems such as suffering from.
Existing reforming catalyst regeneration techniques, as disclosed in USP20120270724, including Burning Coke on Catalyst, chlorination are more
New and reduction.
Reforming catalyst use process needs sulfur content in stringent limitation charging, general to require to be less than 1ppm.If catalysis
Sulfur poisoning occurs for agent use process, and catalyst forms sulfate radical after burning, it is considered that can damage the performance of catalyst.Therefore,
The sulphur before Burning Coke on Catalyst on Removal of catalyst is needed, after usually device stops charging, is removed by the method that hot hydrogen recycles,
In order to avoid sulfate radical is generated in coke combustion, alternatively, needing to remove sulfate radical after the sulfate radical for having generated certain content.
CN98117895.2 discloses a kind of removal methods of sulfate radical on reforming catalyst, at 400~600 DEG C to because of sulphur
Acid group fouled catalyst bed, which is passed through, to be decomposited the organochlorine compound of hydrogen chloride under this condition and is removed, the method compared with
Conventional catalyst chlorination updates regeneration, can sulfate radical effectively in Removal of catalyst.
Summary of the invention
The object of the present invention is to provide a kind of regeneration methods of semi regeneration reforming catalyst, and the catalyst after method regeneration is not
Presulfurization is needed, there is better regeneration effect.
The regeneration method of semi regeneration reforming catalyst provided by the invention, including draw thereto after reclaimable catalyst is made charcoal
Enter sulfate radical, then carries out chlorination update and reduction.
The method of the present invention introduces appropriate sulphur in rear catalyst of making charcoal, and chlorination update and reduction is then carried out again, after regeneration
Catalyst do not need presulfurization, and there is preferable reactivity worth.
Specific embodiment
The method of the present invention is in the regenerative process of semi regeneration catalyst, after making charcoal, introduces into catalyst a certain amount of
The introduction volume of sulphur, sulphur accurately controls, then carries out chlorination update and reduction, makes to be adsorbed in catalyst in reduction process
Sulphur is realized presulfurization in a manner of " autovulcanization ", i.e., carries out presulfurization while reduction.Catalyst use after regeneration is preceding not
Presulfurization is needed, performance is better than the regenerated catalyst of conventional method.
The method of the present invention first makes charcoal reclaimable catalyst, and charcoal temperature is 400~550 DEG C, preferably 450~500 DEG C,
It makes charcoal using oxygen-containing nitrogen, wherein oxygen content is 0.5~21 volume %, preferably 1.0~5.0 volume %.
Catalyst after making charcoal preferably passes through dipping and introduces sulfate radical, accurately to control the introduction volume of sulfate radical.Dipping
The amount for introducing sulfate radical is the sulphur made reclaimable catalyst containing 0.1~1.5 mass %, the sulphur for preferably containing 0.3~0.6 mass %.
In the method for the present invention, dipping is introduced into sulfate radical prepare maceration extract in sulfate radical by sulfuric acid, ammonium sulfate or aluminum sulfate
It provides.Dipping introduces 0.5~2.0 times, preferably 0.8~1.3 times that the maceration extract that sulfate radical is prepared is catalyst volume.Dipping draws
The preference temperature for entering sulfate radical is 50~99 DEG C, preferably 70~90 DEG C, and suitable dip time is 1~24 hour, preferably 2~8
Hour.
In the method for the present invention, dipping introduces sulfate radical preferably using decompression rotary impregnating, by the Reforming catalyst after making charcoal
Agent is fitted into rotatable impregnating autoclave, and being evacuated to pressure is 0.001~0.08MPa (absolute pressure), and prepared maceration extract is added
Enter in impregnating autoclave, temperature is risen into dipping temperature, is preferably to make impregnating autoclave with 1~30 rev/min, preferably 3~10 revs/min
Rate rotation, decompression rotary dipping is carried out, so that sulfate radical is more evenly distributed in catalyst.
After catalyst after dipping introducing sulfate radical is dried in air, roasted, then carry out chlorination update and reduction.It is described
Drying temperature be 70~200 DEG C, preferably 100~150 DEG C, drying time be 1~12 hour, dry roasting, maturing temperature
It is preferred that 400~600 DEG C, calcining time preferably 1~8 hour.
In chlorination renewal process of the present invention, oxygen-containing nitrogen used with making charcoal step, wherein oxygen content preferably 13~
21 volume %, and chlorine-containing compound is injected into oxygen-containing nitrogen, note chlorine dose is 0.1~2.0%, preferably the 0.2 of catalyst quality
~1.0%, it is conventional chlorinating 1.0~1.5 times for updating note chlorine dose.Chlorination update temperature be 400~550 DEG C, preferably 450~
520℃.The chlorine-containing compound is selected from dichloroethanes, trichloroethanes, carbon tetrachloride or tetrachloro-ethylene.
After chlorination updates, restored with hydrogen.In reduction process, hydrogen is preferably passed through under low temperature, then increase temperature into
Row reduction is preferably passed through the temperature of hydrogen not higher than 250 DEG C to catalyst, preferably 150~200 DEG C, then heats to 420
~520 DEG C restore catalyst.
Semi regeneration reforming catalyst of the present invention include alumina support and the content calculated on the basis of carrier such as
Under active component:
0.1~2.0 mass % of platinum,
0.1~2.0 mass % of rhenium,
0.5~5.0 mass % of chlorine.
Yttrium or rare earth metal in the reforming catalyst also containing 0.1~1.0 mass %, the rare earth metal are
Lanthanide series metal, preferably ytterbium, europium or cerium.
The catalyst the preparation method comprises the following steps: be configured to maceration extract by compound containing platinum, containing rhenium compound, contain in maceration extract
There is chlorine, with maceration extract oxide impregnation alumina supporter, by impregnated carrier drying, roasts up to catalyst.The compound containing platinum
It is preferred that chloroplatinic acid, the preferred perrhenic acid containing rhenium compound, the drying temperature are 100~120 DEG C, maturing temperature is 350~650
℃.If containing yttrium or rare earth metal in catalyst, the nitrate or chloride of yttrium or rare earth metal are added in maceration extract.
Below by the example in detail present invention, but the present invention is not limited thereto.
Comparative example 1
PRT-D catalyst (production of middle Effect of Catalysis In Petrochemistry agent Chang Ling branch company) after taking 50g (66mL) coking deactivation, use is oxygen-containing
Amount is that the nitrogen of 0.8 volume % is made charcoal 20 hours, and the catalyst after must making charcoal, composition is shown in Table 1.
Catalyst after making charcoal is packed into 100mL stainless steel tube reactor, is passed through dry air and is pressurized to 1.0MPa, presses
The internal circulating load of 100L/h maintains gas circulation, is warming up to 500 DEG C, and point 5 injection 0.5g dichloroethanes in 4 hours carry out chlorine
Change and updates.It then passes to high pure nitrogen oxygen content into circulating air and is cooled to 200 DEG C less than 0.2 volume %, change logical high-purity hydrogen
Reach 95 volume % to density of hydrogen, then is warming up to 480 DEG C with the internal circulating load of 150L/h and restores 4 hours.400 DEG C are cooled to, note
Enter dimethyl disulfide (DMDS) 0.12g and carry out presulfurization, obtains regenerated catalyst.
Into the reactor of filling regenerated catalyst, with inlet amount (the mass space velocity 2.2h of 110g/h-1) it is passed through composition such as
The purification naphtha of table 2 is warming up to 500 DEG C and reacts 200 hours, liquid product yield before and after the catalyst regeneration of measurement and pungent
Alkane value is shown in Table 3.
Example 1
PRT-D catalyst after taking 50g to make charcoal by 1 method of comparative example, pours into 250mL flask, is evacuated to 0.03MPa
The dilution heat of sulfuric acid that 70mL concentration is 0.007g/mL is added in (absolute pressure), and solution sulfur content is the 0.32% of catalyst quality, with 8
Rev/min rate rotary flask, be warming up to 80 DEG C and impregnate 5 hours, take dipping rear catalyst, in air in 110 DEG C dry 4
Hour, 500 DEG C roast 4 hours.
The catalyst that above-mentioned dipping introduces sulfate radical is packed into 100mL stainless steel tube reactor, dry air is passed through and fills
It is depressed into 1.0MPa, gas circulation is maintained by the internal circulating load of 100L/h, is warming up to 500 DEG C, point 5 injection 0.5g bis- in 4 hours
Chloroethanes carries out chlorination update.It then passes to high pure nitrogen oxygen content into circulating air and is cooled to 200 less than 0.2 volume %
DEG C, change logical high-purity hydrogen to density of hydrogen and reach 95 volume %, then is warming up to 480 DEG C with the internal circulating load of 150L/h and restores 4 hours,
Obtain regenerated catalyst.
400 DEG C are cooled to, into the reactor of filling regenerated catalyst, with inlet amount (the mass space velocity 2.2h of 110g/h-1) it is passed through the purification naphtha of composition such as table 2, it is warming up to 500 DEG C and reacts 200 hours, the liquid before and after the catalyst regeneration of measurement
Product yield and octane number are shown in Table 3.
Example 2
PRT-D catalyst after taking 50g to make charcoal by 1 method of comparative example, pours into 250mL flask, is evacuated to 0.02MPa
The ammonium sulfate that 75mL concentration is 0.012g/mL is added in (absolute pressure), and solution sulfur content is the 0.43% of catalyst quality, rises
Temperature impregnates 4 hours to 85 DEG C, takes dipping rear catalyst, 3 hours dry in 110 DEG C in air, 500 DEG C roast 4 hours.
The catalyst that above-mentioned dipping introduces sulfate radical is packed into 100mL stainless steel tube reactor, dry air is passed through and fills
It is depressed into 1.0MPa, gas circulation is maintained by the internal circulating load of 100L/h, is warming up to 500 DEG C, point 5 injection 0.5g bis- in 4 hours
Chloroethanes carries out chlorination update.It then passes to high pure nitrogen oxygen content into circulating air and is cooled to 200 less than 0.2 volume %
DEG C, change logical high-purity hydrogen to density of hydrogen and reach 95 volume %, then is warming up to 480 DEG C with the internal circulating load of 150L/h and restores 4 hours,
Obtain regenerated catalyst.
400 DEG C are cooled to, into the reactor of filling regenerated catalyst, with inlet amount (the mass space velocity 2.2h of 110g/h-1) it is passed through the purification naphtha of composition such as table 2, it is warming up to 500 DEG C and reacts 200 hours, the liquid before and after the catalyst regeneration of measurement
Product yield and octane number are shown in Table 3.
As known from Table 3, regeneration method of the present invention compared with comparative example 1 conventional regeneration processes, regenerated catalyst have compared with
High liquid product yield and octane number.
Table 1
Table 2
Table 3
Claims (12)
1. a kind of regeneration method of semi regeneration reforming catalyst, including sulfate radical is introduced thereto after reclaimable catalyst is made charcoal,
Chlorination update is carried out again and with hydrogen reducing, the amount that sulfate radical is introduced into rear catalyst of making charcoal is to make reclaimable catalyst containing 0.3
The sulphur of~0.6 mass %.
2. according to the method for claim 1, it is characterised in that the temperature that reclaimable catalyst is made charcoal is 400~550 DEG C, is burnt
Oxygen content in oxygen-containing nitrogen used in charcoal is 0.5~21 volume %.
3. according to the method for claim 1, it is characterised in that made charcoal with dipping normal direction and introduce sulfate radical in rear catalyst, matched
The maceration extract of system is 0.5~2.0 times of catalyst volume.
4. according to the method for claim 3, it is characterised in that sulfate radical is by sulfuric acid, ammonium sulfate or sulphur in the maceration extract of preparation
Sour aluminium provides.
5. according to the method for claim 3, it is characterised in that the temperature that dipping introduces sulfate radical is 20~99 DEG C.
6. according to the method for claim 3, it is characterised in that the pressure that dipping introduces sulfate radical is 0.001~0.08MPa.
7. according to the method for claim 1, it is characterised in that dipping introduce the catalyst after sulfate radical it is dry in air,
Roasting, drying temperature are 70~200 DEG C, and maturing temperature is 400~600 DEG C.
8. according to the method for claim 1, it is characterised in that chlorination update note chlorine dose for catalyst quality 0.1~
2.0%.
9. according to the method for claim 1, it is characterised in that restoring method be not higher than 250 DEG C at a temperature of be passed through hydrogen
Gas is warming up to 420~520 DEG C and is restored.
10. according to the method for claim 1, it is characterised in that the semi regeneration reforming catalyst includes alumina support
The following active component with the content that is calculated on the basis of carrier:
0.1~2.0 mass % of platinum,
0.1~2.0 mass % of rhenium,
0.5~5.0 mass % of chlorine.
11. according to the method for claim 10, it is characterised in that also contain 0.1~1.0 matter in the reforming catalyst
Measure the rare earth metal of %.
12. according to the method for claim 11, it is characterised in that the rare earth metal is yttrium or lanthanide series metal.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510134342.7A CN106140326B (en) | 2015-03-25 | 2015-03-25 | The regeneration method of semi regeneration reforming catalyst |
| TW105109083A TWI681816B (en) | 2015-03-25 | 2016-03-23 | Regeneration method of semi-regeneration recombination catalyst |
| RU2016110754A RU2731273C2 (en) | 2015-03-25 | 2016-03-24 | Method of regenerating partially regenerated reforming catalyst |
| US15/081,234 US9694356B2 (en) | 2015-03-25 | 2016-03-25 | Method for regenerating semi-regenerated reforming catalyst |
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| CN201510134342.7A CN106140326B (en) | 2015-03-25 | 2015-03-25 | The regeneration method of semi regeneration reforming catalyst |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1246517A (en) * | 1998-09-03 | 2000-03-08 | 中国石油化工集团公司 | Process for removing sulfuric acid radial from reforming catalyst |
| CN102371186A (en) * | 2010-08-26 | 2012-03-14 | 中国石油化工股份有限公司 | Reduction method of semi-regenerative reforming catalyst |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8815201B2 (en) * | 2012-05-22 | 2014-08-26 | Chevron U.S.A. Inc. | Process for regenerating a reforming catalyst |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1246517A (en) * | 1998-09-03 | 2000-03-08 | 中国石油化工集团公司 | Process for removing sulfuric acid radial from reforming catalyst |
| CN102371186A (en) * | 2010-08-26 | 2012-03-14 | 中国石油化工股份有限公司 | Reduction method of semi-regenerative reforming catalyst |
Non-Patent Citations (1)
| Title |
|---|
| 硫酸盐硫对铂铼钛重整催化剂反应性能的影响;孙逢铎等;《石油学报（石油加工）》;19880331;第4卷(第1期);第39-45页 |
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