CN108949224A

CN108949224A - A kind of method and its design method and purposes for making heavy oil that there is self-catalysis function

Info

Publication number: CN108949224A
Application number: CN201810742112.2A
Authority: CN
Inventors: 李苏安; 王坤朋; 邓清宇
Original assignee: ZHONGKE CHUANGYI TECH DEVELOPMENT Co Ltd
Current assignee: ZHONGKE CHUANGYI TECH DEVELOPMENT Co Ltd
Priority date: 2018-07-06
Filing date: 2018-07-06
Publication date: 2018-12-07

Abstract

A kind of method and its design method and purposes for making heavy oil that there is self-catalysis function, heavy oil is modified using a kind of modifying agent, make it have self-catalysis function, it is no longer needed in hydrogenator using catalyst, solve that the low bring light oil yield of solid catalyst dispersion degree in hydrogenation technique is low, easy coking at one stroke, and inactivation, poisoning, it is broken, occupy the problems such as reaction compartment.

Description

A kind of method and its design method and purposes for making heavy oil that there is self-catalysis function

Technical field

The present invention relates to a kind of method for making heavy oil have self-catalysis function and its design methods and purposes, belong to oil refiningization Work and coal chemical technology.

Background technique

With the continuous reduction of conventional crude reserves, crude oil heaviness, in poor quality trend are increasingly severe, and the whole world can exploit Crude oil in 70% attach most importance to (bad) matter oil, difficulty of processing is increasing, and pollutant emission in production process is high, and low-quality product is such as Fuel oil, petroleum coke are more, and the atmosphere pollution that these low-quality products generate in use is very serious；Although crude oil heavy increasingly Change, in poor quality, but product oil needs lighting, cleans.On the one hand oil refining enterprise needs to improve light oil yield, increase economical On the other hand benefit is born environmental protection pressure and is gradually increased, needs using more clean technique production product oil and chemicals.Cause This, hydrogen addition technology is increasingly taken seriously, and people develop fixed bed, ebullated bed, slurry bed system (suspension bed) etc. in succession and add hydrogen work Skill.Fixed-bed process no matter processing heavy oil or light distillate, all by following problem perplex: heavy metal can not be processed and asphalitine contains Measure high heavy oil；Catalyst occupies the reaction compartment more than 2/3 or more in the reactor, and catalyst can inactivate or again because of carbon distribution Metal adheres to and is poisoned, and when handling mink cell focus, catalyst life is shorter.The catalyst of boiling bed hydrogenation technique has to last for more Newly, so fluidized bed device requires setting catalyst loading and unloading system, the facility investment is larger, complicated for operation, improves raw material Processing cost, light oil yield are relatively low.Slurry bed system hydrogenation technique can process poor residuum or oily coal mixtures and by favor, But since catalyst with reaction product leaves reactor, catalyst consumption is larger, so various forms of slurry bed systems Hydrogenation technique is generally used cheap iron series solid catalyst.Solid catalyst and feedstock oil are heterogeneous, mixing The device is complicated and mixture homogeneity is limited, and coking caused by causing condensation reaction to increase is serious；Catalyst can wear pump in operation The key equipments such as valve, the shortening device cycle of operation, it is also possible to increase security risk, it is light that part is carried in catalyst separating device Oil reduces light oil yield.Due to the limited activity of this catalyst, reaction temperature and reaction pressure are often higher, this is increased by Plant investment and operating cost.

Summary of the invention

Inventor proposes that one kind makes heavy oil have self-catalysis on the basis of to oil refining process further investigation and technological accumulation The method and its design method and purposes of function, are modified heavy oil using a kind of modifying agent, make it have self-catalysis function, No longer need to that it is light to solve the low bring of solid catalyst dispersion degree in hydrogenation technique at one stroke using catalyst in hydrogenator Oil yield is low, easy coking, and inactivation, poisoning, it is broken, occupy the problems such as reaction compartment.

It is characterized by:

Modifying agent applicable object includes heavy oil (referring to reduced crude, decompression residuum, catalytic slurry, de-oiled asphalt), wax oil, bavin Oil, boat coal and naphtha, coal tar, the mixture of oil and coal dust；Modifying agent uses technique are as follows: after modifying agent is mixed with heavy oil, Boosting, hydrogen is added, heating enters hydrogenator and is reacted, after reaction, modifying agent is with reaction product from anti- It answers in device and flows out, finally there are in the heavy constituent of reaction product；Modifying agent regeneration method are as follows: by modifying agent to be centrifuged, stand Or filtered version is separated from heavy constituent, is allowed to regenerate by hydrogenating reduction and chelating technique.

Self-catalysis technique is added to a kind of modifying agent in oil or oily coal mixtures, and oil or oily coal mixtures is made to add hydrogen There is autocatalysis in reaction, that is, do not need catalyst.

Modifying agent refers to that the organic compound containing one of iron, molybdenum, nickel, cobalt, tungsten or various metals or compound are mixed Zoarium, metallic element ligand are cycloalkane and/or aromatic hydrocarbons, and this metallo-organic compound or compound mixture can be with heavy oil It dissolves each other completely, becomes a part of heavy oil.

Modifying agent adding technology refers in heavy oil into before people's hydrogenator plus people's modifying agent, it is desirable that heavy oil temperature 60~ It 300 DEG C, is uniformly mixed before entering the reactor with static mixer or mechanical mixer, incorporation time 5-90min, additive amount (quality) is 20-3500ppm.

The use technique of modifying agent requires to refer to modifying agent mix with heavy oil after, boost, addition hydrogen, heating up adds into people Hydrogen reactor is reacted, and after reaction, modifying agent is flowed out from reactor with reaction product, and finally there are in reaction In the heavy constituent of product.

Modifying agent regeneration method refers to that be fractionated tower by reaction product is fractionated out respectively by different boiling ranges, by modifying agent with Centrifugation, standing or filtered version are separated from heavy constituent, are allowed to regenerate by hydrogenating reduction and chelating technique.

The technology of the present invention effect is as follows:

The present invention both can be applied to unmanageable heavy oil, oily coal mixtures, can also be applied to wax oil, diesel oil and naphtha The hydrogenation technique of equal distillates, thoroughly gets rid of catalyst and process matched therewith in the hydrogenation process of these materials；Reduce knot Coke extends the reactor cycle of operation；Avoid catalyst because carbon distribution inactivation, because heavy metal adhere to weight poison, because of attrition crushing caused by Hydrogenation capability decline or failure；The space that catalyst occupies in the reactor is reduced, reactor for treatment ability is increased substantially；? When handling the distillates such as wax oil, diesel oil and naphtha, utilization is recycled by modifying agent regeneration technology, reduces production cost, It increases economic efficiency.

Specific embodiment

For the specific features that the present invention is further explained, it is explained below according to embodiment.

The present embodiment is with iron naphthenate for main modifying agent, and molybdenum naphthenate and nickel naphthenate are auxiliary modifier, such as to property Residual oil shown in table 1 is modified, and main modifying agent additive amount is 2000ppm, and auxiliary modifier molybdenum naphthenate and nickel naphthenate add Dosage is respectively 80ppm and 20ppm.

Major-minor modifying agent is stirred in arm stirrer in heating, after temperature reaches 120 DEG C, is stirred 30 minutes, Stirring the frequency is 60 revs/min, is sufficiently mixed modifying agent each component.150 DEG C of residual oil and modifying agent are filled through static mixer It after dividing mixing, boosts to 18MPa, be warming up to 380 DEG C, reacted after being mixed with hydrogen, reaction temperature is 440 DEG C, hydrogen consumption 3.2%, reaction product main character is as shown in tables 2 and 3.

1 Vacuum Residue Properties table of table

Project	Index
		Carbon content wt%	84.83
Hydrogen content wt%	11.16
		Sulfur content wt%	2.93
Nitrogen content wt%	0.77
		Nickel content ppmt	42.2
Content of vanadium ppmt	4.4
		Calcium content ppmt	18.4
Iron content ppmt	8.6
		Hydrogen-to-carbon ratio	1.58
Saturation divides wt%	15.7
		Fragrance divides wt%	33.0
Colloid wt%	45.8
		Heptane Asphaltenes wt%	14.1
Boiling range DEG C	≥520
		Aromatic carbon rate (fa)	0.29
Cycloalkanes carbon rate (fn)	0.23
		Alkyl carbon rate (fp)	0.48
Total number of rings (ft)	9.2
		Number of aromatic nuclei (Ra)	4.9
Cycloalkanes number of rings (Rn)	4.3
		Ra/Rn	1.1

2 product characteristics summary sheet of table

Conclusion:

By embodiment as can be seen that the present invention can carry out heavy oil to be effectively modified, fundamentally changes tradition and urge Change plus hydrogen theory, again without catalysis concept and matched technique for it in hydrogenation technique.

1, since modifying agent can dissolve each other completely with heavy oil, the catalysis efficiency that heavy oil has after the two combines together reaches most Bigization increases substantially the conversion ratio and light oil yield of heavy oil, oily coal mixtures in hydrogenation reaction, reduces condensation reaction, keep away Exempt from coking.Light distillate such as wax oil, diesel oil distillate oil, naphtha cut oil are modified using modifying agent, made it have certainly Catalysis, no longer needed in hydrofinishing addition catalyst, without the concern for catalyst inactivation, poisoning, be crushed the problems such as, release Solid catalyst is released in reactor the space occupied, the useful space of reactor is increased substantially, saves equipment consumptive material.

2, the present invention will solve the problems, such as the whole world weight oil deep processing of (bad) matter, increase substantially crude oil process product oil receipts Rate substantially reduces the atmosphere pollution of oil product in the production and use process to increase economic benefit, lead oil refining industrial upgrading and The development of catalysis industry.

The foregoing is merely preferably one of specific embodiments of the invention, but protection scope of the present invention is not limited to This, any technical staff for being familiar with refining art within the technical scope of the present disclosure, it is contemplated that change or replacement, all contain Lid is within protection scope of the present invention.Therefore, the scope of protection of the invention shall be subject to the scope of protection specified in the patent claim.

Claims

1. modifying agent applicable object includes heavy oil (referring to reduced crude, decompression residuum, catalytic slurry, de-oiled asphalt), wax oil, bavin Oil, boat coal and naphtha, coal tar, the mixture of oil and coal dust；Modifying agent uses technique are as follows: after modifying agent is mixed with heavy oil, Boosting, hydrogen is added, heating enters hydrogenator and is reacted, after reaction, modifying agent is with reaction product from anti- It answers in device and flows out, finally there are in the heavy constituent of reaction product；Modifying agent regeneration method are as follows: by modifying agent to be centrifuged, stand Or filtered version is separated from heavy constituent, is allowed to regenerate by hydrogenating reduction and chelating technique.

2. self-catalysis technique is that a kind of modifying agent is added to right 1 to require in the oily or oily coal mixtures, make oil or oil Coal mixtures have autocatalysis in hydrogenation reaction, that is, do not need catalyst.

3. the modifying agent that claim 2 is previously mentioned is: organising containing one of iron, molybdenum, nickel, cobalt, tungsten or various metals Object or compound mixture are closed, metallic element ligand is cycloalkane and/or aromatic hydrocarbons, and this metallo-organic compound or compound are mixed Zoarium can dissolve each other completely with heavy oil, become a part of heavy oil.

4. the modifying agent adding technology that claim 2 is previously mentioned is: modifying agent is added before heavy oil enters hydrogenator, it is desirable that Heavy oil temperature is uniformly mixed with static mixer or mechanical mixer, incorporation time is before entering the reactor at 60~300 DEG C 5-90min, additive amount (quality) are 20-3500ppm.

5. the use technique for the modifying agent that claim 1 is previously mentioned requires: after modifying agent is mixed with heavy oil, boosting is added Hydrogen, heating enter hydrogenator and are reacted, and after reaction, modifying agent is flowed from reactor with reaction product Out, finally there are in the heavy constituent of reaction product.

6. the modifying agent regeneration method that claim 1 is previously mentioned: being fractionated tower by reaction product and be fractionated respectively by different boiling ranges Out, it by modifying agent to be centrifuged, stand or filtered version is separated from heavy constituent, is allowed to by hydrogenating reduction and chelating technique Regeneration.