CN104560131B

CN104560131B - A kind of semi-regenerating catalytic reforming method

Info

Publication number: CN104560131B
Application number: CN201310507726.XA
Authority: CN
Inventors: 张大庆
Original assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Current assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Priority date: 2013-10-24
Filing date: 2013-10-24
Publication date: 2016-06-22
Anticipated expiration: 2033-10-24
Also published as: CN104560131A

Abstract

A kind of semi-regenerating catalytic reforming method, gas circulation is carried out including starting compressor, Petroleum is sent into semi regeneration reforming reactor, it is warming up to 400～550 DEG C, it is react under 0.2～3.0MPa at pressure, drawing High Purity Hydrogen at suction port of compressor place and be mixed into reforming cycle hydrogen, the high-purity hydrogen of introducing volume flow per hour is 10～1000 times of catalyst volume。This method operating cost is low, easy and simple to handle, can reduce the carbon deposit of course of reaction catalyst, extends catalyst service life。

Description

A kind of semi-regenerating catalytic reforming method

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, it is possible to Petroleum relatively low to octane number or arene content changes into high-knock rating gasoline or the product of high arene content, simultaneously by-product hydrogen。Catalytic reforming process is broadly divided into continuous reforming process and semi regeneration reforming process, and the catalyst of two kinds of technique uses is different。Continuous reforming catalyst uses platinum-tin catalyst, and the activity and selectivity that the feature of this catalyst is the low pressure lower initial stage is good, but less stable, it is necessary to and cyclic regeneration keeps the performance of catalyst。Catalyst is made without presulfurization before use after overactivation, reduction。Semi regeneration reforming catalyst generally uses platinum-rhenium catalyst, and the feature of this catalyst is good stability, and selectivity is slightly worse, it is possible to long period steady running, and the regeneration period can reach 2～3 years。Catalyst needs to carry out presulfurization 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。

Adding additive in reformer feed is a kind of method extending catalyst life。US Patent No. 6478952 is reported, adds AlCl in reformer feed₃Catalyst life can be extended。WO0206426 reports, adds organo-aluminum compound and can also extend catalyst life in reformer feed。

Relying on the method that technique adjustment or optimization improve catalyst life usually improve reaction pressure or increase hydrogen circulation amount in reformer runs, both approaches all reduces catalyst carbon deposit by hydrogen dividing potential drop in raising response system。But appliance arrangement is not only required height by the former, increasing plant investment, and make side reaction increase, so that effectively product yield reduces, the latter then requires that compressor displacement increases, and energy consumption increases。

Summary of the invention

It is an object of the invention to provide a kind of semi-regenerating catalytic reforming method, this method operating cost is low, easy and simple to handle, can reduce the carbon deposit of course of reaction catalyst, extends catalyst service life。

Semi-regenerating catalytic reforming method provided by the invention, gas circulation is carried out including starting compressor, Petroleum is sent into semi regeneration reforming reactor, it is warming up to 400～550 DEG C, it is react under 0.2～3.0MPa at pressure, introducing high-purity hydrogen to mix with reforming cycle hydrogen at suction port of compressor place, the high-purity hydrogen of introducing flow per hour 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 the hydrogen dividing potential drop that can improve in reforming recycle gas, reduces catalyst carbon deposition, extends catalyst service life。

Accompanying drawing explanation

Fig. 1 is reforming reaction method flow schematic diagram of the present invention。

Detailed description of the invention

Reforming reaction is to produce hydrogen rather than consume the process of hydrogen, and high-purity hydrogen is added response system by the present invention through reformer suction port of compressor, to improve circulating hydrogen concentration, and then improves the hydrogen dividing potential drop in reforming recycle gas。The high-purity hydrogen added, in reforming process and be not consumed, but discharges reformer together with the hydrogen produced of reforming。The present invention, when not consuming the high-purity hydrogen of addition, only needs simple adjusting process route to achieve that。Owing to high-purity hydrogen is by reforming reaction system, improves the concentration of reforming cycle hydrogen, thus the hydrogen dividing potential drop that can improve in reforming recycle gas, make catalyst carbon deposit reduce, life。

The purity of high-purity hydrogen of the present invention more than 90 volume %, be preferably greater than 95 volume %。Can for hydrogen used by hydrogenation plant, this high-purity hydrogen can separate, for pressure-variable adsorption, the PSA hydrogen prepared。The high-purity hydrogen introduced in reformer suction port of compressor, improves circulating hydrogen concentration。The high-purity hydrogen added finally discharges system together with the hydrogen produced of reforming, and is transported to hydrogenation plant or the Hydrogen collection device in downstream, as the hydrogen source of hydrogenation reaction。

Introduce in reforming reaction device suction port of compressor 10～1000 times that high-purity hydrogen volume flow hourly is catalyst volume of the inventive method, it is preferable that 20～500 times。

Semi regeneration reforming catalyst of the present invention include alumina support and with the content calculated in reference count for carrier be the platinum of 0.1～0.5 mass %, the chlorine of the rhenium of 0.1～2.0 mass % and 0.5～3.0 mass %。

The present invention is further illustrated below by accompanying drawing。

In Fig. 1, reforming reaction raw material is entered reforming reactor 1 by pipeline 8 and reacts, product enters after 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, fluid product is by bottom line 9 discharger, gas is discharged by overhead line 10, the pipeline 4 being located at compressor 5 porch introduce high-purity hydrogen, enters pipeline 7 and participate in reformed gas circulation after mixing with the hydrogen from pipeline 10 after compressor 5。The high-purity hydrogen introduced can improve the concentration of circulating hydrogen。A part for reforming cycle hydrogen is discharged system by pipeline 6。

The boiling range of Petroleum of the present invention is 40～230 DEG C。Described Petroleum is selected from the mixture of straight run or cracking gasoline or the cracking of its admixture heat or the gasoline of catalytic cracking, partial conversion Petroleum or dehydrogenation Petroleum 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。

Using the CB-70 catalyst (productions of Chang Ling catalyst plant) of presulfurization, carrier is gama-alumina, with the active component content of calculation in reference count for aluminium oxide in Table 1。Take 50mlCB-70 and load 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, making gas/catalyst volume ratio is 2000/1, pressure is 1.0MPa, with the ramp of 30 DEG C/h to 370 DEG C, injects reforming reaction raw material by the inlet amount of 100ml/h in reactor, with the ramp of 30 DEG C/h to 500 DEG C, introduce the purity high-purity hydrogen for 99 volume % with the flow of 2.5L/h from pipeline 4。Reformation product hydrogen and the hydrogen filled into through pipeline 4 are discharged through pipeline 6, and output is about 25.5L/h。Operate 500 hours, measure reaction result。Reaction raw materials used forms in Table 2, and reaction result is in Table 3。

Example 2

Reforming reaction is carried out, the difference is that being introduced, with the flow of 10L/h, the high-purity hydrogen that purity is 99 volume % by pipeline 4 by the method for example 1。Reformation product hydrogen and the hydrogen filled into through pipeline 4 are discharged through pipeline 6, and output is about 33L/h。The reaction result operated 500 hours is in Table 3。

Comparative example 1

Carrying out reforming reaction by the method for example 1, the difference is that not introducing high-purity hydrogen at pipeline 4, the reaction result operated 500 hours is in Table 3。

Table 3 is it is shown that the inventive method is compared with the comparative example 1 being not introduced into high-purity hydrogen, and the activity and selectivity of reforming catalyst improves, and catalyst carbon deposit reduces, and catalyst extends service life。

Table 1

Table 2

Hydrocarbon carbon number	Alkane, quality %	Cycloalkane, 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

1. a semi-regenerating catalytic reforming method, gas circulation is carried out including starting compressor, Petroleum is sent into semi regeneration reforming reactor, it is warming up to 400～550 DEG C, it is react under 0.2～3.0MPa at pressure, introducing high-purity hydrogen to mix with reforming cycle hydrogen at suction port of compressor place, 20～500 times that high-purity hydrogen volume flow hourly is catalyst volume of introducing, the purity of described high-purity hydrogen is more than 95 volume %。

2. in accordance with the method for claim 1, it is characterised in that described semi regeneration reforming catalyst include alumina support and with the content calculated in reference count for carrier be the platinum of 0.1～0.5 mass %, the chlorine of the rhenium of 0.1～2.0 mass % and 0.5～3.0 mass %。

3. in accordance with the method for claim 1, it is characterised in that the boiling range of Petroleum is 40～230 DEG C。

4. in accordance with the method for claim 3, it is characterised in that described Petroleum is straight run or the mixture of cracking gasoline or the cracking of its admixture heat or the gasoline of catalytic cracking, partial conversion Petroleum or dehydrogenation Petroleum composition。