CN103285859B - A kind of sulphided state multimetal reforming catalyst and preparation method thereof - Google Patents
A kind of sulphided state multimetal reforming catalyst and preparation method thereof Download PDFInfo
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Abstract
A kind of many metals sulphided state catalyst for reforming naphtha, comprise high-temperature inorganic oxide carrier and the platinum group metal of to take carrier as the content of benchmark be 0.05 ~ 2.0 quality %, the VIIB race metal of 0.05 ~ 2.0 quality %, the 3rd metal constituent element of 0.01 ~ 2.0 quality %, the halogen of 0.05 ~ 5.0 quality % and the sulphur of 0.15 ~ 0.3 quality %, the sulfur content of described catalyst and the mass ratio of theoretical sulfur content are 1.8 ~ 3.0, and the 3rd described metal constituent element is lanthanide series metal or yttrium.In this catalyst, sulfur content is higher, and the reduction of catalyst and sulfuration are combined into a step, both simplifies preparation process, and turn improves catalyst performance.
Description
Technical field
The present invention is a kind of catalyst for reforming naphtha and preparation method thereof, specifically, is multimetal reforming catalyst for half-regeneration reformer of a kind of sulphided state and preparation method thereof.
Background technology
Catalytic reforming be a kind of produce high octane value gasoline blending component or produce as important petrochemical materials light aromatics (benzene,toluene,xylene) and the technical process of cheap hydrogen is provided.In recent years, along with the increasingly stringent of environmental requirement, the fast development of polyester industrial, and petroleum refining industry is to the growth of hydrogen demand and improving constantly oil quality requirement, the production capacity of catalytic reforming unit increases year by year, and wherein semi regenerative reformer is in occupation of very consequence.
Semi regeneration reforming catalyst is mainly platinum-rhenium catalyst, needs to carry out drying activation, reduction and presulfurization before using.Most of moisture in carrier hole is sloughed in dry activation, and metal precursor is changed into the chlorinity of corresponding oxide and adjustment catalyst.Reduction makes the oxidation state platinum on catalyst that the metallic state platinum being converted into high dispersive occur to reduce, and makes catalyst have more high activity.Rhenium metal on catalyst has very high hydrogenolysis activity, must carry out presulfurization process before the reaction to catalyst.If do not carried out sulfuration to catalyst before the reaction, there is strong hydrogenolysis by the oil-feed initial stage, releasing a large amount of reaction heat, reaction bed temperature is raised rapidly, occurs overheating problem.Light then cause a large amount of carbon deposit of catalyst, the activity of infringement catalyst and stability, heavy then burn out catalyst and reactor.Therefore semi regeneration reforming catalyst must carry out presulfurization before use; generate sulfuration rhenium to make the rhenium metal on catalyst and reaction of Salmon-Saxl thus suppress the hydrogenolysis activity of rhenium on catalyst and deep dehydrogenation active; the activity of guard catalyst and stability, improve the selective of catalyst.
At present, the mode of platinum rhenium semi regeneration reforming catalyst being carried out to presulfurization has two kinds: (1) be catalyst after hydrogen reducing, in hydrogen, inject a certain amount of H
2s, slowly carries out presulfurization to reduction-state catalyst under certain temperature, pressure; (2) be catalyst after hydrogen reducing, reduction-state catalyst injects organic sulfur compound at uniform temperature, pressure with when facing hydrogen, as dimethyl disulfide, dimethyl sulfide etc., these organic sulfur compounds decompose after form H
2s carries out presulfurization to catalyst.Mode (1) is generally used for laboratory research, and mode (2) is commonly used to commercial plant and goes into operation.The essence of these two kinds of modes is all use H
2s carries out presulfurization to catalyst, all belongs to gas-phase presulfiding.Hayes etc. (JCatal.1975,37:553 ~ 554) find that above-mentioned presulfurization obviously can reduce Pt/A1
2o
3the coke deposit rate of reforming catalyst, the cycle lie of extending catalyst.Ramaswamy (Proc.Inc.Congr.Catal.6
th, 1976,2:1061 ~ 1070) although think that the dehydrogenation activity of metal active centres declines after reforming catalyst sulfuration, very stable; Although unvulcanized catalyst initial activity is very high, due to excessive dehydrogenation, the rapid carbon deposit of catalyst, deactivation rate is fast, poor stability.
CA748409A carries out presulfurization with the gas of sulfur-bearing to the reforming catalyst containing Pt before oil-feed, presulfurization is carried out under low sulfur content and high gas flow rate condition, can make sulfide equably with catalyst exposure, the sulfur content in sulfuration rear catalyst is 0.01 ~ 0.03w%.The sulfide that presulfurization uses is hydrogen sulfide or the sulfur-containing compound that can decompose under conditions of vulcanization, and as disulphide or carbon disulfide etc., this presulfurization can be used for fresh dose, also can be used for regenerated catalyst.Regenerated catalyst after presulfurization, comparatively has same sulfur content, but obviously reduces without the coke content of the regenerated catalyst of presulfurization.
CA1125211, USP4220520 disclose a kind of Al containing Ir
2o
3the method that reforming catalyst goes into operation, described catalyst also can comprise platinum, and this catalyst all needs to carry out presulfurization before use.Presulfurization is with containing a certain amount of H
2the hydrogen of S processes catalyst, then purges catalyst by pure hydrogen gas, and remove wherein unnecessary sulphur, the sulfur content of sulfuration rear catalyst is up to 0.07wt%, and catalytic activity and stability are all improved.
RU2370315C
2disclose a kind of vulcanization process, platinum-rhenium reforming catalyst in pure hydrogen in 480 ~ 500 DEG C of reductase 12 ~ 4h, then sulfuration is carried out in two stages, first stage cure temperature is 480 ~ 400 DEG C, second stage is 280 ~ 260 DEG C, and sulfuration gas is the hydrogen containing sulfide (sulfur content is 0.05 ~ 0.3 quality %).
Summary of the invention
The object of this invention is to provide a kind of sulphided state multimetal reforming catalyst and preparation method thereof, in this catalyst, sulfur content is higher, and the reduction of catalyst and sulfuration are combined into a step, both simplifies preparation process, and turn improves catalyst performance.
Sulphided state multimetal reforming catalyst provided by the invention, comprise high-temperature inorganic oxide carrier and the platinum group metal of to take carrier as the content of benchmark be 0.05 ~ 2.0 quality %, the VIIB race metal of 0.05 ~ 2.0 quality %, the 3rd metal constituent element of 0.01 ~ 2.0 quality %, the halogen of 0.05 ~ 5.0 quality % and the sulphur of 0.15 ~ 0.3 quality %, the sulfur content of described catalyst and the mass ratio of theoretical sulfur content are 1.8 ~ 3.0, and the 3rd described metal constituent element is lanthanide series metal or yttrium.
The present invention, by oxidation state semi regeneration multimetal reforming catalyst, uses sulfur-bearing hydrogen treat, first adsorbs sulphur at a lower temperature, then carries out reducing and sulfuration under higher temperature simultaneously, eliminate the step of at high temperature reducing with pure hydrogen.Obtained catalyst no longer needs presulfurization in start-up process, directly with reformer feed haptoreaction, can curtailment of operation reduce operating procedure, and hydrocarbon reformation is reacted there is higher reactivity and arenes selectivity.
Detailed description of the invention
Sulphided state semi regeneration multimetal reforming catalyst provided by the invention is under oxidized catalyst nitrogen is purged displacement to substantially oxygen-free situation, the sulfur-bearing hydrogen that direct use contains appropriate sulphur compound processes a period of time at low temperatures, oxidized catalyst is made to adsorb sulphur, improving temperature again makes the catalyst of absorption sulphur have reduction under sulfide existent condition and sulfuration, and described sulfuration is carried out mainly for VIIB race metal.The sulphided state catalyst sulfur content that the sulphided state catalyst obtained is prepared compared with conventional method is many, and catalytic performance improves, catalyst preparing also more conventional method for pre-sulphuration simplification simultaneously.
In described sulphided state catalyst, sulfur content is 0.15 ~ 0.23 quality % preferably.Described platinum group metal is Pt, Pd, Ru, Rh, Ir, Os, preferred platinum, the preferred rhenium of VIIB race metal, the preferred ytterbium of the 3rd metal constituent element lanthanide series metal, samarium or neodymium, the preferred chlorine of halogen, high-temperature inorganic oxide carrier preferential oxidation aluminium.The sulphur quality of the theoretical sulfur content of described catalyst needed for sulfuration VIIB race metal, calculates theoretical sulfur content (S
t) time, think that sulfuration is only carried out for VIIB race metal, in catalyst, platinum group metal and the 3rd metal constituent element do not participate in vulcanization reaction, and VIIB race metal and sulphur by 1: 1 atomic ratio carry out vulcanization reaction.
The preparation method of sulphided state semi regeneration multimetal reforming catalyst provided by the invention comprises the steps:
(1) the oxidation state multimetal reforming catalyst of platinum group metal, VIIB race metal, the 3rd metal constituent element and halogen is loaded reactor, hydrogen is passed in reactor, beds is warming up to 100 ~ 250 DEG C, sulfide is injected in hydrogen, with sulfur-bearing hydrogen treat catalyst at least 0.5 hour, in described sulfur-bearing hydrogen, sulfur content counts 100 ~ 3000 μ L/L with hydrogen sulfide, and the 3rd described metal constituent element is lanthanide series metal or yttrium
(2) beds is warming up to 450 ~ 550 DEG C, continues to use sulfur-bearing hydrogen treat 1 ~ 10 hour, obtain sulphided state multimetal reforming catalyst.
In said method, (1) step is processed with the hydrogen containing sulfide at low temperatures by oxidation state multimetal reforming catalyst, makes it adsorb sulphur.First oxidation state multimetal reforming catalyst is loaded reactor, apply nitrogen metathesis reactor and connecting line before passing into hydrogen, oxygen free gas remaining in catalyst is cemented out, to ensure handling safety.When in nitrogen displacement to discharge gas, oxygen content is less than 50 μ L/L, hydrogen can be passed into, start beds to heat up simultaneously, reaction bed temperature reach 100 ~ 250 DEG C, preferably 150 ~ 200 DEG C time, sulfide is injected in hydrogen, carry out K cryogenic treatment at this temperature, the time of process beds is preferably 0.8 ~ 2.0 hour.In described sulfur-bearing hydrogen, sulfur content is preferably 400 ~ 1200 μ L/L in hydrogen sulfide.
(1) the oxidation state multimetal reforming catalyst described in step is semi regeneration reforming catalyst, the preferred platinum in platinum group metal wherein, the preferred rhenium of VIIB race metal, the preferred ytterbium of the 3rd metal constituent element lanthanide series metal, samarium or neodymium, the preferred chlorine of halogen, high-temperature inorganic oxide carrier preferential oxidation aluminium.
Described method (2) step is at high temperature, reduces and presulfurization with the catalyst of sulfur-bearing hydrogen to (1) step process.Preferably reaction bed temperature is risen to 400 ~ 530 DEG C, then undertaken reducing and presulfurization by sulfur-bearing hydrogen treat, preferably 2 ~ 8 hours processing time, more preferably 2 ~ 6 hours.
Described oxidation state multimetal reforming catalyst adopts conventional infusion process preparation, with the impregnation fluid high-temperature inorganic oxide carrier of platinum group metal, VIIB race metal, the 3rd metal constituent element and halogen, drier, roasting.Prepare the preferred chloroplatinic acid of compound of maceration extract platinum group metal used, ammonium choroplatinate, bromoplatinic acid, tri-chlorination platinum, platinum tetrachloride hydrate, dichloride hydroxyl platinum, dinitro diaminourea platinum tetranitro sodium platinate (II) (Sodiumtetranitroplatinate (II)), palladium bichloride, palladium nitrate, palladium sulfate, diaminourea palladium hydroxide (diamminepalladium (II) hydroxide), chlorine four ammonia palladium (tetramminepallaclium (II) chloride), chlorine six ammonia palladium, chlorination hydroxyl rhodium, rhodium chloride hydrate, rhodium nitrate, chlordene rhodium acid sodium (Sodiumhexachlororhodate (III)), hexanitro rhodium acid sodium (Sodiumhexanitrorhodate (III)), chloro-iridic acid, tribromide iridium, iridochloride, iridic chloride, hexanitro iridium acid sodium (Sodiumhexanitroridate (III)), potassium hexachloroiridate, iridium sodium chloride, oxalic acid rhodium potassium.Preferred chloroplatinic acid.The preferred perrhenic acid of compound of VIIB race metal used or ammonium perrhenate.3rd metal constituent element is its nitrate preferably, and the baking temperature of impregnated carrier is 100 ~ 150 DEG C, and preferably 6 ~ 24 hours drying time, sintering temperature is 400 ~ 800 DEG C, preferably 2 ~ 24 hours time.
In said method, by the gas of beds, namely the volume ratio of hydrogen or sulfur-bearing hydrogen and catalyst is 300 ~ 1500, preferably 600 ~ 1200: 1.Described sulfur-bearing hydrogen is the hydrogen of the organic sulfur compound that maybe can decomposite hydrogen sulfide containing hydrogen sulfide, the preferred dimethyl disulfide of described organic sulfur compound, dimethyl sulfide or carbon disulfide.
Sulphided state multimetal reforming catalyst provided by the invention, does not need to carry out sulfuration separately again before catalyst reaction, can directly and hydrocarbon raw material haptoreaction.
Catalyst of the present invention is suitable for the catalytic reforming reaction of naphtha.Naphtha is the whole-distillate gasoline of boiling range 40 ~ 230 DEG C, as the mixture of the gasoline of straight run and cracking gasoline or its admixture heat cracking or catalytic cracking, partial conversion naphtha or dehydrogenation naphtha composition.Reforming reaction condition is: 0.1 ~ 10.0MPa, preferably 0.3 ~ 2.5MPa, 370 ~ 600 DEG C, preferably 450 ~ 550 DEG C, hydrogen/hydrocarbon mol ratio 1 ~ 20, preferably 2 ~ 10, feedstock quality air speed 0.1 ~ 20.0 hour
-1, preferably 0.5 ~ 5.0 hour
-1.
Further illustrate the present invention below by example, but the present invention is not limited to this.
Example 1
(1) oxidized catalyst is prepared
Get 50 grams of γ-Al
2o
3carrier, maceration extract is made into chloroplatinic acid, perrhenic acid, yttrium nitrate and hydrochloric acid, Gu make liquid/volume ratio be 1.3, platiniferous 0.20 quality %, rhenium 0.40 quality %, yttrium 0.20 quality % and chlorine 1.5 quality % (all calculating relative to butt aluminium oxide) in maceration extract.Carrier is placed in reduced pressure atmosphere, makes pressure be 0.02MPa, maintain 0.5 hour, stop decompression operation, introduce maceration extract, flood 3 hours under 30 DEG C of rotating conditions, 60 DEG C, 0.02MPa Rotary drying 1 hour.After dipping, solids was in 120 DEG C of dryings 12 hours.In dry air, in 500 DEG C, gas/solid volume ratio be the condition of 700 under roasting 4 hours, obtain oxidized catalyst.
(2) sulphided state catalyst is prepared
Oxidized catalyst is packed into reactor, passes into nitrogen displacement air wherein, after the oxygen content of Exhaust Gas is less than 50 μ L/L, think that displacement is qualified, pass into hydrogen, controlling gas/solid volume ratio is 800: 1.Starting beds to heat up gradually, when reaction bed temperature reaches 120 DEG C, in hydrogen, inject hydrogen sulfide, make hydrogen sulfide content in hydrogen be 500 μ L/L, is process catalyst 1 hour under the condition of 800: 1,120 DEG C in gas/solid volume ratio.Reaction bed temperature is warming up to 460 DEG C gradually, continues at this temperature by hydrogen sulfide containing hydrogen treat 4 hours.Reaction bed temperature is down to 25 DEG C, changes logical nitrogen, purge after 0.5 hour, draw off catalyst, sealing is preserved, and obtains catalyst A, and its composition is in table 1.
Example 2
Prepare sulphided state catalyst by example 1 method, during unlike (1) step preparation maceration extract, replace yttrium nitrate with ytterbium nitrate, the composition of the sulphided state catalyst B finally obtained is in table 1.
Example 3
Prepare sulphided state catalyst by example 1 method, during unlike (1) step preparation maceration extract, replace yttrium nitrate with samaric nitrate, the composition of the sulphided state catalyst C finally obtained is in table 1.
Example 4
Prepare sulphided state catalyst by example 1 method, during unlike (1) step preparation maceration extract, replace yttrium nitrate with neodymium nitrate, the composition of the sulphided state catalyst D finally obtained is in table 1.
Example 5
Oxidized catalyst is prepared by example 1 (1) one step process, sulphided state catalyst is prepared again by (2) one step process, after passing into hydrogen unlike nitrogen displacement is qualified, by beds heat temperature raising, when reaction bed temperature reaches 180 DEG C, hydrogen sulfide is injected, with hydrogen sulfide containing hydrogen 180 DEG C of process 1 hour in hydrogen.And then reaction bed temperature is risen to 460 DEG C, continue by hydrogen sulfide containing hydrogen treat 4 hours.After cooling and nitrogen purge, the composition of the catalyst E obtained is in table 1.
Example 6
Oxidized catalyst is prepared by example 1 (1) one step process, sulphided state catalyst is prepared again by (2) one step process, after passing into hydrogen unlike nitrogen displacement is qualified, by beds heat temperature raising, when reaction bed temperature reaches 250 DEG C, hydrogen sulfide is injected, with hydrogen sulfide containing hydrogen 250 DEG C of process 1 hour in hydrogen.And then reaction bed temperature is risen to 460 DEG C, continue by hydrogen sulfide containing hydrogen treat 4 hours.After cooling and nitrogen purge, the composition of the catalyst F obtained is in table 1.
Example 7
Oxidized catalyst is prepared by example 1 (1) one step process, sulphided state catalyst is prepared again by (2) one step process, after passing into hydrogen unlike nitrogen displacement is qualified, by beds heat temperature raising, when reaction bed temperature reaches 180 DEG C, in hydrogen, inject dimethyl disulfide, it is 1000 μ L/L that the injection rate of dimethyl disulfide to make in hydrogen in the sulfur content of hydrogen sulfide, with the hydrogen containing dimethyl disulfide 180 DEG C of process 1 hour.Then reaction bed temperature is risen to 460 DEG C, continue by the hydrogen treat 4 hours containing dimethyl disulfide.After cooling and nitrogen purge, the composition of the catalyst G obtained is in table 1.
Comparative example 1
Oxidized catalyst is prepared by example 1 (1) one step process, oxidized catalyst is packed into reactor, passes into nitrogen displacement air wherein, after the oxygen content of Exhaust Gas is less than 50 μ L/L, pass into hydrogen, controlling gas/solid volume ratio is 800: 1.Beds is warming up to 460 DEG C gradually, and uses hydrogen reducing at this temperature 4 hours.Again reaction bed temperature is down to 425 DEG C, in hydrogen, injects hydrogen sulfide, make hydrogen sulfide content in hydrogen be 500 μ L/L, vulcanizing treatment is carried out 1 hour to catalyst, stop injecting hydrogen sulfide, continue purging 2 hours with hydrogen.Reaction bed temperature is down to 25 DEG C, changes logical nitrogen and purge 0.5 hour, draw off catalyst, sealing is preserved.The catalyst R obtained
1composition in table 1.
Comparative example 2
Oxidized catalyst is prepared by example 1 (1) one step process, oxidized catalyst is packed into reactor, passes into nitrogen displacement air wherein, after the oxygen content of Exhaust Gas is less than 50 μ L/L, pass into hydrogen, controlling gas/solid volume ratio is 800: 1.Beds is warming up to 350 DEG C gradually, in hydrogen, injects hydrogen sulfide, make hydrogen sulfide content in hydrogen be 500 μ L/L, process 1 hour with this understanding.Reaction bed temperature is continued to rise to 460 DEG C again, and at this temperature by hydrogen sulfide containing hydrogen treat 4 hours.Reaction bed temperature is down to 25 DEG C, changes logical nitrogen and purge 0.5 hour, draw off catalyst, sealing is preserved.The catalyst R obtained
2sulfur content in table 1.
Example 8
The catalyst prepare the present invention and the reactivity worth of comparative catalyst are evaluated.
In the reactor of micro anti-evaluation device, load 1mL catalyst, pass into normal heptane and react, control that reactor inlet temperature is 500 DEG C, reaction pressure is 1.0MPa, mass space velocity is 3.0 hours
-1, hydrogen/hydrocarbon mol ratio is 5.5: 1, reaction result is in table 2.
From table 2 data, catalyst of the present invention, than comparative catalyst, has higher conversion ratio and aromatics yield, illustrates that catalyst of the present invention has higher activity and arenes selectivity.
Table 1
S
tfor theoretical sulfur content
Table 2
Claims (11)
1. a sulphided state multimetal reforming catalyst, comprise high-temperature inorganic oxide carrier and the platinum group metal of to take carrier as the content of benchmark be 0.05 ~ 2.0 quality %, the rhenium of 0.05 ~ 2.0 quality %, the 3rd metal constituent element of 0.01 ~ 2.0 quality %, the halogen of 0.05 ~ 5.0 quality % and the sulphur of 0.15 ~ 0.3 quality %, the sulfur content of described catalyst and the mass ratio of theoretical sulfur content are 1.8 ~ 3.0, and the 3rd described metal constituent element is lanthanide series metal or yttrium.
2., according to catalyst according to claim 1, it is characterized in that the sulfur content in described catalyst is 0.15 ~ 0.23 quality %.
3., according to catalyst according to claim 1, it is characterized in that described platinum group metal is platinum, halogen is chlorine, and lanthanide series metal is ytterbium, samarium or neodymium, and high-temperature inorganic oxide carrier is aluminium oxide.
4. a preparation method for catalyst described in claim 1, comprises the steps:
(1) the oxidation state multimetal reforming catalyst of platinum group metal, rhenium, the 3rd metal constituent element and halogen is loaded reactor, hydrogen is passed in reactor, beds is warming up to 100 ~ 250 DEG C, sulfide is injected in hydrogen, with sulfur-bearing hydrogen treat catalyst at least 0.5 hour, in described sulfur-bearing hydrogen, sulfur content counts 100 ~ 3000 μ L/L with hydrogen sulfide, and the 3rd described metal constituent element is lanthanide series metal or yttrium
(2) beds is warming up to 450 ~ 550 DEG C, continues to use sulfur-bearing hydrogen treat 1 ~ 10 hour, obtain sulphided state multimetal reforming catalyst.
5. in accordance with the method for claim 4, it is characterized in that the platinum group metal described in (1) step is platinum, lanthanide series metal is ytterbium, samarium or neodymium, and halogen is chlorine, and the carrier of oxidation state multimetal reforming catalyst is aluminium oxide.
6. in accordance with the method for claim 4, it is characterized in that, in (1) step, beds is warming up to 150 ~ 200 DEG C, then inject sulfide in hydrogen, in described sulfur-bearing hydrogen, sulfur content counts 500 ~ 1200 μ L/L with hydrogen sulfide.
7. in accordance with the method for claim 4, to it is characterized in that in (1) step with the time of sulfur-bearing hydrogen treat beds being 0.8 ~ 2.0 hour.
8. in accordance with the method for claim 4, it is characterized in that described sulfide is hydrogen sulfide or organic sulfur compound.
9. in accordance with the method for claim 8, it is characterized in that described organic sulfur compound is dimethyl disulfide, dimethyl sulfide or carbon disulfide.
10. in accordance with the method for claim 4, it is characterized in that, in (2) step, reaction bed temperature is risen to 450 ~ 530 DEG C, then use sulfur-bearing hydrogen treat 2 ~ 6 hours.
11. in accordance with the method for claim 4, it is characterized in that by the gas of beds and the volume ratio of catalyst be 300 ~ 1500.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4046711A (en) * | 1976-06-24 | 1977-09-06 | Uop Inc. | Method of catalyst manufacture |
| CN1465665A (en) * | 2002-06-27 | 2004-01-07 | 中国石油化工股份有限公司 | Method for preparing polymetallic reforming catalyst |
| CN101468313A (en) * | 2007-12-28 | 2009-07-01 | 中国石油化工股份有限公司 | Method for preparing reforming catalyst |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4046711A (en) * | 1976-06-24 | 1977-09-06 | Uop Inc. | Method of catalyst manufacture |
| CN1465665A (en) * | 2002-06-27 | 2004-01-07 | 中国石油化工股份有限公司 | Method for preparing polymetallic reforming catalyst |
| CN101468313A (en) * | 2007-12-28 | 2009-07-01 | 中国石油化工股份有限公司 | Method for preparing reforming catalyst |
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