CN104560131A - Semi-regenerative catalytic reforming method - Google Patents
Semi-regenerative catalytic reforming method Download PDFInfo
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- CN104560131A CN104560131A CN201310507726.XA CN201310507726A CN104560131A CN 104560131 A CN104560131 A CN 104560131A CN 201310507726 A CN201310507726 A CN 201310507726A CN 104560131 A CN104560131 A CN 104560131A
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- hydrogen
- reforming
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- catalyst
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Classifications
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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
- C10G35/00—Reforming naphtha
- C10G35/04—Catalytic reforming
- C10G35/06—Catalytic reforming characterised by the catalyst used
- C10G35/085—Catalytic reforming characterised by the catalyst used containing platinum group metals or compounds thereof
- C10G35/09—Bimetallic catalysts in which at least one of the metals is a platinum group metal
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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
- C10G2300/10—Feedstock materials
- C10G2300/1037—Hydrocarbon fractions
- C10G2300/1044—Heavy gasoline or naphtha having a boiling range of about 100 - 180 °C
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- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention discloses a semi-regenerative catalytic reforming method, comprising the following steps: starting a compressor to carry out gas circulation, feeding naphtha to a semi-regenerative reforming reactor, heating to 400-550 DEG C, and reacting under 0.2-3.0MPa; introducing high-purity hydrogen at the inlet of the compressor, and mixing with reforming cycle hydrogen, wherein the volume flow per hour of the introduced high-purity hydrogen is 10-1000 times volume of the catalyst. The method is low in operation cost and simple and convenient to operate; carbon deposit of a catalyst in the reaction process can be reduced; and the service life of the catalyst is prolonged.
Description
Technical field
The present invention is a kind of catalystic reforming method for hydrocarbons, specifically, is a kind of semi-regenerating catalytic reforming method.
Background technology
Catalytic reforming is a kind of important oil refining process, octane value or the lower convert naphtha of aromaticity content can be become the product of stop bracket gasoline or high aromaticity content, by-product hydrogen simultaneously.Catalytic reforming process is mainly divided into continuous reforming process and semi regeneration reforming process, and the catalyzer of two kinds of technique uses is different.Continuous reforming catalyst uses platinum-tin catalyst, and the feature of this catalyzer is that the activity and selectivity at low pressure lower initial stage is good, but less stable, need cyclic regeneration to keep the performance of catalyzer.Catalyzer does not need to carry out prevulcanized before use after overactivation, reduction.Semi regeneration reforming catalyst generally uses platinum-rhenium catalyst, and the feature of this catalyzer is good stability, and selectivity is slightly poor, can long period steady running, and the regeneration period can reach 2 ~ 3 years.Catalyzer needs to carry out prevulcanized before use after overactivation, reduction.
In reforming process, reduce catalyst carbon deposit and can extend the reforming catalyst life-span, improve reformer on-road efficiency.
A kind of method that additive is the extending catalyst life-span is added in reformer feed.US Patent No. 6478952 is reported, in reformer feed, add AlCl
3can the extending catalyst life-span.WO0206426 reports, in reformer feed, add organo-aluminium compound also can the extending catalyst life-span.
In reformer runs, rely on technique adjustment or optimize the method improving catalyst life and normally improve reaction pressure or increase hydrogen circulation amount, these two kinds of methods all reduce catalyst carbon deposit by improving hydrogen dividing potential drop in reactive system.But the former not only requires high to appliance arrangement, increase plant investment, and side reaction is increased, thus effective product yield is reduced, latter requires that compressor discharge rate increases, and energy consumption increases.
Summary of the invention
The object of this invention is to provide a kind of semi-regenerating catalytic reforming method, this method running cost is low, easy and simple to handle, can reduce the carbon deposit of reaction process catalyzer, extending catalyst work-ing life.
Semi-regenerating catalytic reforming method provided by the invention, comprise startup compressor and carry out gas circulation, petroleum naphtha is sent into semi regeneration reforming reactor, be warming up to 400 ~ 550 DEG C, react under pressure is 0.2 ~ 3.0MPa, introduce high-purity hydrogen to mix with reforming cycle hydrogen at suction port of compressor place, the high-purity hydrogen flow per hour of introducing is 10 ~ 1000 times of catalyst volume.
The inventive method, in semi regeneration reforming process, introduces one high-purity hydrogen in suction port of compressor place, improves circulating hydrogen concentration, thus can improve the hydrogen dividing potential drop in reforming recycle gas, reduces catalyst carbon deposition, extending catalyst work-ing life.
Accompanying drawing explanation
Fig. 1 is reforming reaction method flow schematic diagram of the present invention.
Embodiment
Reforming reaction is the process producing hydrogen instead of consume hydrogen, and high-purity hydrogen is added reactive system through reformer suction port of compressor by the present invention, to improve circulating hydrogen concentration, and then improves the hydrogen dividing potential drop in reforming recycle gas.The high-purity hydrogen added, is not consumed in reforming process, but discharges reformer together with the hydrogen that produces reformed.The present invention, under the condition not consuming the high-purity hydrogen added, only needs simple adjusting process route just can realize.Because high-purity hydrogen is by reforming reaction system, improves the concentration of reforming cycle hydrogen, thus the hydrogen dividing potential drop in reforming recycle gas can be improved, catalyst carbon deposit is reduced, life.
The purity of high-purity hydrogen of the present invention is greater than 90 volume %, is preferably greater than 95 volume %.Can be hydrogenation unit hydrogen used, this high-purity hydrogen can be pressure-variable adsorption and is separated obtained PSA hydrogen.The high-purity hydrogen introduced in reformer suction port of compressor, improves circulating hydrogen concentration.Discharge system together with the hydrogen that the high-purity hydrogen added finally produces with reformation, be transported to hydrogenation unit or the Hydrogen collection device in downstream, as the hydrogen source of hydrogenation reaction.
The high-purity hydrogen volumetric flow rate hourly that the inventive method is introduced in reforming reaction device suction port of compressor is 10 ~ 1000 times of catalyst volume, preferably 20 ~ 500 times.
Semi regeneration reforming catalyst of the present invention comprises alumina supporter and take carrier as the content of benchmark is the chlorine of the platinum of 0.1 ~ 0.5 quality %, the rhenium of 0.1 ~ 2.0 quality % and 0.5 ~ 3.0 quality %.
The present invention is further illustrated below by accompanying drawing.
In Fig. 1, reforming reaction raw material enters reforming reactor 1 by pipeline 8 and reacts, reaction product enters after water cooler 2 carries out heat exchange cooling after being discharged by reforming reactor 1, enter gas-liquid separator 3 and carry out gas-liquid separation, liquid product is by bottom line 9 discharger, gas is discharged by overhead line 10, introduces high-purity hydrogen by the pipeline 4 being located at compressor 5 ingress, enters pipeline 7 participate in reformed gas and circulate with the hydrogen from pipeline 10 after mixing after compressor 5.The high-purity hydrogen introduced can improve the concentration of circulating hydrogen.A part for reforming cycle hydrogen discharges system by pipeline 6.
The boiling range of petroleum naphtha of the present invention is 40 ~ 230 DEG C.Described petroleum naphtha is selected from the mixture of the gasoline of straight run or pressure gasoline or its admixture heat cracking or catalytic cracking, partial conversion petroleum naphtha or dehydrogenation petroleum naphtha composition.
Further illustrate the present invention below by example, but the present invention is not limited to this.
Example 1
Reforming reaction is carried out by the flow process of Fig. 1.
Use the CB-70 catalyzer (production of Chang Ling catalyst plant) of prevulcanized, carrier is gama-alumina, is that the active component content of benchmark is in table 1 with aluminum oxide.Getting 50ml CB-70 loads in reactor, the high-purity hydrogen that purity is 99 volume % is introduced by pipeline 4, exchange system is also pressurized to 1.0MPa, stops introducing hydrogen, starts compressor cycle, gas/catalyst volume ratio is made to be 2000/1, pressure is 1.0MPa, with the ramp to 370 DEG C of 30 DEG C/h, injects reforming reaction raw material by the inlet amount of 100ml/h in reactor, with the ramp to 500 DEG C of 30 DEG C/h, introduce from pipeline 4 high-purity hydrogen that purity is 99 volume % with the flow of 2.5L/h.Reform and produce hydrogen and discharge through pipeline 6 through the hydrogen that pipeline 4 fills into, output is about 25.5L/h.Operate 500 hours, measure reaction result.Reaction raw materials composition used is in table 2, and reaction result is in table 3.
Example 2
Carry out reforming reaction by the method for example 1, introduce with the flow of 10L/h the high-purity hydrogen that purity is 99 volume % unlike by pipeline 4.Reform and produce hydrogen and discharge through pipeline 6 through the hydrogen that pipeline 4 fills into, output is about 33L/h.The reaction result operated 500 hours is in table 3.
Comparative example 1
Carry out reforming reaction by the method for example 1, unlike not introducing high-purity hydrogen at pipeline 4, the reaction result operated 500 hours is in table 3.
Table 3 result shows, the inventive method is compared with the comparative example 1 not introducing high-purity hydrogen, and the activity and selectivity of reforming catalyst improves, and catalyst carbon deposit reduces, and catalyzer extends work-ing life.
Table 1
Table 2
| Hydrocarbon carbon number | Alkane, quality % | Naphthenic hydrocarbon, quality % | Aromatic hydrocarbons, quality % |
| 5 | 0.28 | - | - |
| 6 | 16.83 | 5.07 | 0.36 |
| 7 | 17.47 | 7.55 | 1.69 |
| 8 | 17.17 | 6.93 | 2.59 |
| 9 | 10.32 | 5.49 | 1.80 |
| 10 | 5.39 | 0.91 | 0.15 |
Table 3
Claims (7)
1. a semi-regenerating catalytic reforming method, comprise startup compressor and carry out gas circulation, petroleum naphtha is sent into semi regeneration reforming reactor, be warming up to 400 ~ 550 DEG C, react under pressure is 0.2 ~ 3.0MPa, introduce high-purity hydrogen to mix with reforming cycle hydrogen at suction port of compressor place, the high-purity hydrogen volumetric flow rate hourly of introducing is 10 ~ 1000 times of catalyst volume.
2. in accordance with the method for claim 1, it is characterized in that the high-purity hydrogen volumetric flow rate hourly introduced is 20 ~ 500 times of catalyst volume.
3. in accordance with the method for claim 1, it is characterized in that the purity of described high-purity hydrogen is greater than 90 volume %.
4. in accordance with the method for claim 1, it is characterized in that the purity of described high-purity hydrogen is greater than 95 volume %.
5. the chlorine of in accordance with the method for claim 1, it is characterized in that described semi regeneration reforming catalyst comprises alumina supporter and to take carrier as the content of benchmark the be platinum of 0.1 ~ 0.5 quality %, the rhenium of 0.1 ~ 2.0 quality % and 0.5 ~ 3.0 quality %.
6. in accordance with the method for claim 1, it is characterized in that the boiling range of petroleum naphtha is 40 ~ 230 DEG C.
7. in accordance with the method for claim 6, it is characterized in that described petroleum naphtha is the mixture of the gasoline of straight run or pressure gasoline or its admixture heat cracking or catalytic cracking, partial conversion petroleum naphtha or dehydrogenation petroleum naphtha composition.
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| CN201310507726.XA CN104560131B (en) | 2013-10-24 | 2013-10-24 | A kind of semi-regenerating catalytic reforming method |
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| CN201310507726.XA CN104560131B (en) | 2013-10-24 | 2013-10-24 | A kind of semi-regenerating catalytic reforming method |
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| CN104560131A true CN104560131A (en) | 2015-04-29 |
| CN104560131B CN104560131B (en) | 2016-06-22 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106753548A (en) * | 2015-11-21 | 2017-05-31 | 中国石油化工股份有限公司 | A kind of Benzin naphtha catalytic reforming method of by-product also protohydrogen |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3520800A (en) * | 1968-09-30 | 1970-07-14 | Universal Oil Prod Co | Purifying hydrogen gas effluent from a catalytic reforming process |
| US4208397A (en) * | 1976-12-20 | 1980-06-17 | Standard Oil Company (Indiana) | Semi-regenerative reforming process providing continuous hydrogen production |
| CN102796553A (en) * | 2011-05-27 | 2012-11-28 | 中国石油化工股份有限公司 | Catalytic reforming method for naphtha |
| US20130020233A1 (en) * | 2011-05-27 | 2013-01-24 | Aizeng Ma | Processes for catalytically reforming naphtha |
-
2013
- 2013-10-24 CN CN201310507726.XA patent/CN104560131B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3520800A (en) * | 1968-09-30 | 1970-07-14 | Universal Oil Prod Co | Purifying hydrogen gas effluent from a catalytic reforming process |
| US4208397A (en) * | 1976-12-20 | 1980-06-17 | Standard Oil Company (Indiana) | Semi-regenerative reforming process providing continuous hydrogen production |
| CN102796553A (en) * | 2011-05-27 | 2012-11-28 | 中国石油化工股份有限公司 | Catalytic reforming method for naphtha |
| US20130020233A1 (en) * | 2011-05-27 | 2013-01-24 | Aizeng Ma | Processes for catalytically reforming naphtha |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106753548A (en) * | 2015-11-21 | 2017-05-31 | 中国石油化工股份有限公司 | A kind of Benzin naphtha catalytic reforming method of by-product also protohydrogen |
| CN106753548B (en) * | 2015-11-21 | 2018-08-14 | 中国石油化工股份有限公司 | A kind of Benzin naphtha catalytic reforming method of by-product also protohydrogen |
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| CN104560131B (en) | 2016-06-22 |
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