CN103725308A

CN103725308A - Catalyst regeneration method capable of reducing carbon dioxide discharge

Info

Publication number: CN103725308A
Application number: CN201210385658.XA
Authority: CN
Inventors: 许友好; 王新; 李首先; 龚剑洪
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: 2012-10-12
Filing date: 2012-10-12
Publication date: 2014-04-16
Anticipated expiration: 2032-10-12
Also published as: CN103725308B

Abstract

The invention discloses a catalyst regeneration method capable of reducing carbon dioxide discharge. The catalyst regeneration method is characterized in that a catalyst with coke goes up in a coke combustion pipe by being carried by pure oxygen and undergoes a coke combustion reaction, and the coke combustion ratio in a coke combustion pipe is in a range of 30-50%; the catalyst discharged from the coke combustion pipe is subjected to pure oxygen-based residual coke burning; after cyclone separation, flue gas is orderly fed into a flue gas energy recovery system and a carbon dioxide separation system; after carbon dioxide separation, a capturing process is carried out; and the regenerated catalyst is directly returned into a reactor for recycle. The catalyst regeneration method realizes complete regeneration of a catalyst and uniform distribution of catalyst activity so that coke as a catalytic cracking by-product and a dry gas yield are reduced. The catalyst regeneration method greatly reduces carbon emission and even realizes zero emission of carbon.

Description

A kind of catalyst regeneration process that reduces Carbon emission

Technical field

The present invention relates to the renovation process containing Pd/carbon catalyst in a kind of hydrocarbon processing process.More particularly, the present invention relates to realize in mink cell focus catalytic cracking process the catalyst regeneration process of carbon dioxide discharge-reduction.

Background technology

Now, whole world petroleum refining industry development faces the lot of challenges such as oil price fluctuation, the aggravation of crude oil in poor quality trend, oil quality specification improve, energy-saving and emission-reduction requirement becomes sternly, biofuel develops rapidly, and minimizing Carbon emission, mitigation of climate change have become petroleum refining industry transforms mode of economic growth, keeps the only way of Sustainable development.In October, 2009, country has announced the action target of controlling greenhouse gas emission, arrives the year two thousand twenty nationwide units gross domestic product CO ₂discharge declined 40% to 45% than 2005, and clearly proposed per GDP carbon dioxide emission reduction 17% during " 12 ", and country likely imposes " carbon tax " during " 12 " in good time simultaneously.Therefore in refining of petroleum and chemical process, effectively reduce carbon emission and seem and be even more important, trap, seal up for safekeeping and manage CO ₂refinery's vital task in future will be become.Carbon emission in heavy oil upgrading process is mainly the carbon emission of catalytic cracking burning, hydrogen production process and the energy consumption of technological process.Catalytic cracking unit is the core production equipment of refinery, because catalyzer burns, becomes CO ₂one of main source of discharge.

US2011/0155642A1 discloses a kind of catalytic cracking process process that reduces Carbon emission, adopt coke-burning riser series connection dense bed regenerating unit, pure oxygen and the regeneration techniques in coke-burning riser multiple spot delivery of supplemental oxygen, this technology Special attention will be given to has increased a tank at regeneration circuit and circuit to be generated respectively, it is degassed that the tank of circuit of wherein regenerating adopts nitrogen to carry out regenerated catalyst, and the tank of circuit to be generated burns efficiency by temperature before introducing spent agent and regenerated catalyst and mixing to improve reclaimable catalyst regeneration to improve.But the introducing of regeneration circuit nitrogen finally inevitably can make nitrogen play a reversed role in flue gas by revivifier, obviously lost the advantage of pure oxygen regeneration, only burn efficiency and increase, but the recovery of carbonic acid gas has increased difficulty.

US4542114 discloses a kind of integral process process that reclaims the flue gas compositions such as carbonic acid gas, can realize and in burning process, go back hydrogen manufacturing and carbon dioxide product, eliminate sulphur, the aerial discharge of oxynitride completely, its pure oxygen mixed gas that adopts carbonic acid gas to dilute carries out catalyzer and burns to produce rich carbonated flue gas simultaneously.But this technique does not increase interior heat collecting device for realizing in revivifier, emphasize wherein the preferred 30-24% of oxygen concentration 60-21% in mixed gas, thereby part has lost the advantage that adopts purity oxygen regeneration, burns efficiency as increased substantially, and reduces revivifier size etc.

US5565089 discloses a kind of catalytic cracking catalyst process of regenerating, first with air, to enter revivifier to carry out catalyzer and burn, then the carbonic acid gas in reclaiming flue gas, recycled carbon dioxide and be incorporated to gradually oxygen-containing gas stream until in revivifier temperature normal, last direct oxygen injection and carbonic acid gas carry out burning of catalyzer.This process of regenerating is only paid close attention to the improvement of regenerative process inlet system aspect and the processing of flue gas, does not consider the problem of the aspects such as revivifier structure or concrete reclaiming process process and catalytic cracking catalyst circulation.

CN1600431A discloses a kind of incomplete regen-eration smoke combustion technology, employing supplements the way of air in the incomplete regen-eration stack gas between catalyst regenerator and flue gas turbine inlet, CO in incomplete regen-eration flue gas is burnt away, thereby make flue-gas temperature be increased to 660-760 ℃, finally make flue gas turbine inlet temperature reach 640-700 ℃, improve cigarette machine organic efficiency, thereby reduce plant energy consumption with recovered flue gas pressure energy to greatest extent.Adopt the present invention, according to the concentration of unit scale and CO and/or entraining hydrocarbon, supplement air capacity 20-300Nm ³/ min, can effectively improve flue-gas temperature 20-80 ℃, improves cigarette engine efficiency.For single hop incomplete regen-eration, in flue, supplement air and also can make flue gas carry hydro carbons secretly fully to burn, eliminate its impact on cigarette machine, but can not effectively reduce CO2 emissions.

Because conventional catalyzer coke burning regeneration method is to pass into air or oxygen-containing gas is regenerated in fluidized-bed, and air is mainly by O ₂and N ₂composition, contains a large amount of N in the regenerated flue gas therefore producing after catalyzer coke burning regeneration ₂, CO ₂with a small amount of O ₂and CO.And the flue gas of this composition is due to CO ₂concentration is low, therefore CO ₂separating difficulty is large, cost is high, cannot be isolated collection, can only enter directly discharge after energy-recuperation system, thereby cause Greenhouse effect.

In addition,, from the development of regenerator, pursue the at utmost recovery that realizes regenerated catalyst activity, to realize the maximum conversion ability of hydro carbons always.But the activity of catalyzer is the concept represent of a macroscopical transformation efficiency, does not embody the pursuit of object product selectivity.While for example regenerating, can realize regenerated catalyst activation recovering the highest, but this regenerated catalyst may be because its high reactivity causes high coke and dry gas yied when participating in reaction, this does not wish to see.While therefore regenerating, need to pursue a kind of homogeneity that catalyst activity recovers, realize in other words on regenerated catalyst acid one and be uniformly distributed, thereby realize low coke and dry gas yied, high object product selectivity.Therefore, be necessary to develop a kind of reduction Carbon emission and improve optionally catalyst regeneration process.

Summary of the invention

The object of the invention is to provide on the basis of existing technology a kind of catalyst regeneration process that reduces Carbon emission.

The catalyst regeneration process of reduction Carbon emission provided by the invention adopts the regenerating unit pattern of coke-burning riser series connection dense bed, and coke-burning riser is for carrying bed operation, and dense bed is bubbling bed operation, and the method comprises:

(1) up in coke-burning riser under pure oxygen gas carries from the band Pd/carbon catalyst of catalytic cracking unit stripping stage, there is coke combustion reactions, the ratio of burning in coke-burning riser is 30-50%;

(2) dense-phase bed that catalyzer out and flue gas enter regenerating unit from coke-burning riser, dense-phase bed bottom further supplements purity oxygen, the catalyzer of incomplete regen-eration is further burnt in dense-phase bed, holomorphosis, the ratio of burning of dense-phase bed is 50-70%;

(3) dense-phase bed need to arrange heat collector, to control the temperature of dense-phase bed, is no more than 750 ℃ and is preferably no more than 720 ℃;

(4) to dense-phase bed, supplement or replenishment cycles flue gas not, when replenishment cycles flue gas, keep oxygen concentration from revivifier cyclone separation system flue gas to be out not less than 30% and be preferably not less than 40%;

(5) flue gas enters smoke energy recovering system after cyclonic separator separates, and enters subsequently carbon dioxide separating system, after separating carbon dioxide, traps, and the direct Returning reactor of regenerated catalyst recycles.

The operational condition of described coke-burning riser is: temperature 600-750 ℃, catalyzer mean residence time are 2.0-60.0 second, and preferably 5.0-40.0 second, the gas superficial linear velocity of coke-burning riser is 1.0-4.0m/s, is preferably 1.2-3.0m/s.

The operational condition of described dense-phase bed is: dense-phase bed operates in bubbling bed, and temperature 600-750 ℃, catalyzer mean residence time are 1.0-5.0 minute, preferably 1.0-4.0 minute, and gas superficial linear velocity is 0.4-0.8m/s, is preferably 0.4-0.6m/s.The heat collector of dense-phase bed setting is interior heat collector or/and external warmer, and heat collector is one or more.

Described catalyzer comprises zeolite, inorganic oxide and optional clay, and each component accounts for respectively total catalyst weight and is: the heavy % of the heavy %-50 of zeolite 1, the heavy % of the heavy %-99 of inorganic oxide 5, the heavy % of the heavy %-70 of clay 0.Its mesolite is active ingredient, be selected from mesopore zeolite and/or optional large pore zeolite, mesopore zeolite accounts for the heavy % of 10 heavy %-100 of zeolite gross weight, the preferably heavy % of 20 heavy %-80, large pore zeolite accounts for the heavy % of 0 heavy %-90 of zeolite gross weight, the preferably heavy % of 20 heavy %-80.Mesopore zeolite is selected from one or more mixtures and/or the ZRP zeolite in ZSM series zeolite, also can carry out modification to the transition metal such as the non-metallic elements such as phosphorus and/or iron, cobalt, nickel for above-mentioned mesopore zeolite.Large pore zeolite selects one or more the mixture in this group zeolite that super steady Y, high silicon Y that free Rare Earth Y (REY), rare earth hydrogen Y (REHY), different methods obtain form.

Inorganic oxide, as support of the catalyst, is selected from silicon-dioxide and/or aluminium sesquioxide or both mixtures.

Clay, as caking agent, is selected from one or more in kaolin, polynite, diatomite, saponite, rectorite leng, sepiolite, hydrotalcite and wilkinite.

Compared with existing renovation process, major advantage of the present invention is following two aspects:

1, the method not only can make catalyzer holomorphosis, can significantly reduce carbon emission simultaneously, and even zero carbon emission reduces Greenhouse effect.

2, the method can significantly reduce especially revivifier reserve of device catalyst inventory, greatly reduces the size of static equipment and moving equipment, reduces investment, reduces floor space.

3, because purity oxygen concentration in regeneration system rapidly is high, thereby make to burn efficiency, increase substantially, the recovery time shortens, and reduces fragmentation, the wearing and tearing of catalyzer, has improved the service efficiency of catalyzer.

Accompanying drawing explanation

Accompanying drawing is the catalyst regeneration process schematic flow sheet of reduction Carbon emission provided by the invention.

Embodiment

Below in conjunction with accompanying drawing, further illustrate method provided by the present invention, but the present invention is not therefore subject to any restriction.

In accompanying drawing, each numbering is described as follows:

1,10,11,12,13,18,20,21 all represent pipeline; 2 is coke-burning riser; 3 is revivifier; 4 is dense-phase bed; 5 is freeboard of fluidized bed; 6 and 17 are cyclone separation system; 8 is smoke energy recovering system; 9 is carbon dioxide separating system; 14 is riser reactor; 15 is stripping stage; 16 is settling vessel; 19 is oil and gas separating system; 22 is external warmer.

As shown in drawings, reclaimable catalyst enters coke-burning riser 2 through inclined tube 1 to be generated, pure oxygen gas enters coke-burning riser 2 through pipeline 20, contact concurrent green coke charcoal combustion reactions, up with reclaimable catalyst, flue gas and incomplete regen-eration catalyzer enter the dense-phase bed 4 of revivifier 3, purity oxygen also enters the bottom of dense-phase bed 4 through pipeline 21, thereby the catalyzer of incomplete regen-eration is further burnt, regenerate.For controlling the temperature of dense-phase bed, be provided with external warmer 22.The flue gas of dense-phase bed through revivifier freeboard of fluidized bed 5, cyclone separation system 6 leaves revivifier.From a revivifier flue gas part out, directly enter smoke energy recovering system 8 recovered energies, another part returns to the bottom of dense-phase bed 4 through pipeline 10 circulations, can realize the lifting of the carbon dioxide in flue gas concentration that enters carbon dioxide separating system 9.From energy-recuperation system 8 flue gas out, enter carbon dioxide separating system 9, realize the trapping of carbonic acid gas.Regenerated catalyst after regeneration enters riser reactor 14 bottoms through regenerator sloped tube 11, it is up that pre-lift medium enters riser reactor bottom lifting regenerated catalyst through pipeline 12, stock oil enters riser reactor through pipeline 13 and contacts with regenerated catalyst and carry out catalytic cracking reaction, and reaction oil gas enters oil and gas separating system 19 through settling vessel 16, cyclone separation system 17 and gas pipeline 18 successively and obtains various products.Reclaimable catalyst enters inclined tube 1 to be generated and turns back to coke-burning riser 2 and regenerate after stripping stage 15 strippings, thereby realize, recycles.

The following examples will be further described the present invention, but not thereby limiting the invention.The stock oil using in embodiment and comparative example is vacuum residuum, and its character is listed in table 1.Catalyzer is produced by catalyzer branch office of Sinopec Group Shandong catalyst plant, and goods number is MLC-500, and its character is listed in table 2.

Embodiment

Embodiment carries out on catalytic cracking demonstration unit, as shown in drawings.Demonstration unit does not have smoke energy recovering system and carbon dioxide separating system.Wherein 5 centimetres of the internal diameters of coke-burning riser, the internal diameter of dense-phase bed is 50 centimetres.According to renovation process proposed by the invention, catalyzer is regenerated, at coke-burning riser and dense-phase bed, pass into respectively pure oxygen gas, from revivifier cyclone separation system flue gas partial out, return to dense-phase bed bottom simultaneously.The middle part temperature of coke-burning riser is 640 ℃, and revivifier dense-phase bed temperature is 650 ℃.Catalyzer is 12 seconds in the residence time of coke-burning riser, at the mean residence time of dense-phase bed, is 2 minutes.In coke-burning riser, gas superficial linear velocity is 1.5m/s, and in dense-phase bed, gas superficial linear velocity is 0.5m/s.Catalyzer after regeneration enters reactor, and the stock oil listed with table 1 contacts, and carries out catalytic cracking reaction, and regeneration condition, reaction conditions, regenerated catalyst carbon content and flue gas composition are all listed in table 3.

Comparative example

Comparative example is also to carry out on the catalytic cracking demonstration unit of same structure, but the internal diameter of coke-burning riser and dense bed is different, 15 centimetres of the internal diameters of coke-burning riser, and the internal diameter of dense-phase bed is 200 centimetres, other scantlings of the structure is identical with embodiment.Pair reclaimable catalyst identical with embodiment of renovation process routinely regenerated, and coke-burning riser and dense-phase bed pass into respectively air, and the middle part temperature of coke-burning riser is 600 ℃, and revivifier dense-phase bed temperature is 680 ℃.Catalyzer is 12 seconds in the residence time of coke-burning riser, at the mean residence time of dense-phase bed, is 10 minutes.In coke-burning riser, gas superficial linear velocity is 1.5m/s, and in dense-phase bed, gas superficial linear velocity is 0.5m/s.Catalyzer after regeneration enters reactor, and the stock oil listed with table 1 contacts, and carries out catalytic cracking reaction, and regeneration condition, reaction conditions, regenerated catalyst carbon content and flue gas composition are all listed in table 3.

From the result contrast of operational condition and table 3, can find out, compared with comparative example, the present invention significantly reduces, installs general reserve in coke-burning riser size and regeneration dense bed size and significantly reduces, consumes under the obvious prerequisite reducing of wind index, adopt renovation process proposed by the invention, on regenerated catalyst, carbon content reduces more, in addition in the flue gas that, this catalyst regeneration process produces, do not contain CO and N ₂, gas concentration lwevel, up to 58%, is conducive to separation and the trapping of carbonic acid gas.

Table 1

Stock oil title	Vacuum residuum
		Density (20 ℃), kg/m ³	920.9
Kinematic viscosity, millimeter ²/ second
		100℃	114.4
Carbon residue, heavy %	8.2
		Condensation point, ℃	25
Total nitrogen, heavy %	0.33
		Sulphur, heavy %	0.21
Carbon, heavy %	86.91
		Hydrogen, heavy %	12.55
Metal content, ppm
		Nickel	8.8
Vanadium	0.1
		Iron	1.8
Copper	＜0.1
		Sodium	3.0
Boiling range, ℃
		HK (initial boiling point)	415
10％	545
		30％	/
50％	/
		70％	/
KK (final boiling point)	/

Table 2

Catalyzer goods number	MLC-500
		Chemical constitution, heavy %
Aluminum oxide	50.2
		Sodium oxide	0.321
Apparent density, kg/m ³	700
		Pore volume, mL/g	0.38
Specific surface area, m ²/g	229
		Abrasion index, during heavy % ^-1	1.9
Size composition, heavy %
		0～40 micron	17.3
40～80 microns	49.3
		80 microns of >	33.4

Table 3

	Embodiment	Comparative example
			Device catalyzer general reserve, ton	0.8	4
Cracking hydrocarbon reaction member
			Outlet temperature of riser, ℃	500	500
Catalyst/feed weight ratio	6	6
			Reaction times, second	3	3
Water vapor/raw material weight ratio	0.05	0.05
			Regeneration unit
Coke-burning riser internal diameter, cm	5	15
			Dense bed internal diameter, cm	50	200
Consumption wind index, Nm ³/kg	4	15
			Carbon content on regenerated catalyst, heavy %	0.04	0.08
Regenerated flue gas composition, %
			N ₂	0	79.5
CO ₂	58.22	15.37
			CO	0	4.36
O ₂	41.78	0.77

Claims

1. reduce a catalyst regeneration process for Carbon emission, it is characterized in that the method adopts the regenerating unit pattern of coke-burning riser series connection dense bed, coke-burning riser is for carrying bed operation, and dense bed is bubbling bed operation, and the method comprises:

(3) dense-phase bed need to arrange heat collector, to control the temperature of dense-phase bed, is no more than 750 ℃;

(4) to dense-phase bed, supplement or replenishment cycles flue gas not, when replenishment cycles flue gas, keep the oxygen concentration from revivifier cyclone separation system flue gas to be out not less than 30%;

2. according to the method for claim 1, it is characterized in that the operational condition of described coke-burning riser is: temperature 600-750 ℃, catalyzer mean residence time is 2.0-60.0 second, gas superficial linear velocity is 1.0-4.0m/s.

3. according to the method for claim 2, it is characterized in that the operational condition of described coke-burning riser is: catalyzer mean residence time is 5.0-40.0 second, and gas superficial linear velocity is 1.2-3.0m/s.

4. according to the method for claim 1, it is characterized in that the operational condition of described dense-phase bed is: temperature 600-750 ℃, catalyzer mean residence time is 1.0-5.0 minute, gas superficial linear velocity is 0.4-0.8m/s.

5. according to the method for claim 4, it is characterized in that the operational condition of described Second reactivator is: catalyzer mean residence time is 1.0-4.0 minute, gas superficial linear velocity is 0.4-0.6m/s.

6. according to the method for claim 1, it is characterized in that the described heat collector of step (3) is interior heat collector or/and external warmer, heat collector is one or more.

7. according to the method for claim 1, it is characterized in that the temperature of step (3) control dense-phase bed is no more than 720 ℃.

8. according to the method for claim 1, it is characterized in that the oxygen concentration in the described flue gas of step (4) is not less than 40%.

9. according to the method for claim 1, it is characterized in that described catalyzer comprises zeolite, inorganic oxide and optional clay, each component accounts for respectively total catalyst weight and is: the heavy % of the heavy %-50 of zeolite 1, the heavy % of the heavy %-99 of inorganic oxide 5, the heavy % of the heavy %-70 of clay 0.