CN105623279B

CN105623279B - A kind of preparation method of mediation pitch

Info

Publication number: CN105623279B
Application number: CN201410603835.6A
Authority: CN
Inventors: 刘树华; 郭皎河
Original assignee: China Petroleum and Chemical Corp; Sinopec Fushun Research Institute of Petroleum and Petrochemicals
Current assignee: China Petroleum and Chemical Corp; Sinopec Fushun Research Institute of Petroleum and Petrochemicals
Priority date: 2014-11-03
Filing date: 2014-11-03
Publication date: 2018-04-10
Anticipated expiration: 2034-11-03
Also published as: CN105623279A

Abstract

The invention discloses a kind of preparation method of mediation pitch, including following content：（1）Gasoline alkaline residue, aminated compounds, which are added in slurry oil, heats blending and modifying, obtains being modified slurry oil；（2）Modified slurry oil is added in the asphalt stock of molten state and reconciled, obtains slurry oil mediation pitch.Mediation pitch prepared by this method has higher penetration ratio.The present invention expands application approach of the slurry oil resource in pitch, is advantageous to improve the utilization benefit of slurry oil.Meanwhile also it have found an environmentally friendly method for the processing of alkaline residue.

Description

A kind of preparation method of mediation pitch

Technical field

The present invention relates to a kind of preparation method of mediation pitch, and in particular to a kind of gasoline alkaline residue is modified slurry oil mediation pitch Preparation method.

Background technology

Gasoline alkaline residue derives from gasoline（Constant pressure gasoline, FCC gasoline）Alkali refining, its COD be up to it is tens thousand of to 100,000, If do not handled discharge, environment can be seriously polluted.

At present, domestic oil plant typically uses sulfuric acid or CO₂Deng sour gas neutralisation, gasoline refining alkaline residue is carried out Pretreatment, as CN201110313313.9 uses N₂/SO₂Mixed gas is handled alkaline residue.Though these methods can reclaim alkali Crude phenols, neutral oil, organic acid in slag waste water etc., but due to lacking advanced treating measure, can not thoroughly solve high concentration Shock problem of the alkaline sewage to sewage treatment plant.Therefore, gasoline alkaline residue is the general character pollutant of domestic refinery's generally existing, is One big difficult point of oil refining enterprise's wastewater treatment.

FCC is one of important secondary operation technique of oil plant, and its working ability is in Chinese oil plant secondary operation head Position.With the heaviness increasingly of FCC feedstock, oil plant externally extracting oil amount is increasing, commonly reaches the 5% ~ 10% of its processing capacity. Slurry oil arene content is high, and generally more than 50%, therefore a kind of rich fragrant raw material of poor wax is generally considered to be, it can be used as and improve ductility Effective blend component, for this many people carried out reconcile pitch experiment and industrial production.

The limitation that most of Chinese Crude Oils are belonged to due to its base, it is relatively low to produce pitch mostly Ductility ratio, therefore, many researchs With component of the production unit using slurry oil as increase bitumen ductility, carry out road asphalt experimental study and production, slurry oil are applied to Road asphalt mainly includes following several method at present（1）Slurry oil is distilled, obtains heavy slurry oil, then with residual oil or de- Oil asphalt or oxidized asphalt reconcile, and prepare road asphalt product；（2）With carrying out solution-off together with residual oil, obtained de-oiled asphalt is made For road asphalt or its blend component；（3）A number of FCC slurry is added in crude oil or reduced crude, carries out condistillation（Institute Call intensifying distillation）, obtain road asphalt.

Slurry oil mediation pitch subject matter is the thin film oven of mediation pitch（TFOT）Penetration ratio is relatively low afterwards, it is difficult to meet The road asphalt product requirement of higher level.It can thus be seen that penetration ratio has turned into influences slurry oil in road asphalt application In major obstacle.

The content of the invention

In view of the shortcomings of the prior art, it is an object of the invention to provide a kind of preparation method of mediation pitch, by this Mediation pitch prepared by method has higher penetration ratio.

The preparation method of the mediation pitch of the present invention, including following content：

（1）Gasoline alkaline residue, aminated compounds, which are added in slurry oil, heats blending and modifying, obtains being modified slurry oil；

（2）Modified slurry oil is added in the asphalt stock of molten state and reconciled, obtains slurry oil mediation pitch.

In the inventive method, described gasoline alkaline residue can be that the alkali cleaning of constant pressure gasoline cut, FCC gasoline cut refines alkali The mixture of one or both of slag, preferably FCC gasoline alkaline residue.

In the inventive method, described aminated compounds is aromatic amine, fatty amine and multiethylene polyamine, preferred fat amine, More preferably C₁₂~C₁₈Fatty amine.

In the inventive method, described gasoline alkaline residue is preferred before use to carry out dewater treatment, makes its water content in 10wt% Hereinafter, preferably below 5wt%.Water content determination method is GB/T 8929-2006.

In the inventive method, described slurry oil be distillate catalytic cracked oil pulp, reduced crude catalysis slurry oil, residual oil catalysis split Carburetion is starched or distillate mixes the one or more refined in RFCC slurry oil；Wherein described residual oil includes reduced crude, subtracted The heavy oil that pressure residual oil, crude oil are handled through plug, distillate include vacuum gas oil (VGO)（VGO）And AGO (atmospheric gas oil)（AGO）.Slurry oil is Normal pressure bottom stream, therefore using it as pitch blend component, generally require and carry out plug processing, selected boiling range scope >400 DEG C, preferably>420℃.

In the inventive method, described asphalt stock is the one or more of road asphalt, residual oil and de-oiled asphalt.

In the inventive method, gasoline alkaline residue addition accounts for the 0.5% ~ 12% of slurry oil weight, preferably 3% ~ 10%.

In this inventive method, aminated compounds addition accounts for the 0.05% ~ 5% of slurry oil weight, preferably 0.2% ~ 1.0%。

In the inventive method, the harmonic proportion of modified slurry oil is generally 5% ~ 40%（Account for mediation pitch gross mass）, preferably Ratio is 10% ~ 30%.Within this range, needle penetration of the modified addition also with asphalt stock enters with the pin required by mediation pitch Spend relevant.In other words, smaller, the resulting mediation Asphalt Penetration of the needle penetration of asphalt stock requires bigger, and modified slurry oil makes Dosage is bigger.

The inventive method can also be carried out as follows：Step（1）In obtained modification slurry oil first pass through at plug Reason, then carries out step again（2）Pitch harmonic process；Wherein being modified the boiling range scope after slurry topping processing is>400 DEG C, It is preferred that>420℃.

In the inventive method, step（1）Hybrid reaction temperature be 70~160 DEG C, preferably 100~150 DEG C, the reaction time For 10~120 minutes, preferably 30~60 minutes；Step（2）Mediation temperature be 130 ~ 160 DEG C, reconcile the time be 10~120 Minute, preferably 30~60 minutes；Step（1）And step（2）Process carry out under agitation, using routine machinery Stirring, the mixed medias such as ultrasound, high shear or colloid mill can also be used.

In the inventive method, step（1）The hybrid reaction of middle gasoline alkaline residue and slurry oil can be carried out in open-top receptacle, also may be used With reaction with pressure, preferably closed container in closed container.

The inventive method is modified to slurry oil by adding gasoline refining alkaline residue and aminated compounds in slurry oil, Slurry oil property is improved, carries out pitch mediation with modified slurry oil, obtained product has higher penetration ratio, while is also vapour The processing and application of oily alkaline residue provide an environmentally friendly utilization ways.

Embodiment

The present invention program and effect are further illustrated with reference to embodiment, but and are not so limited the present invention.

Embodiment 1

The true boiling point distillation devices of FY- III produced using Fushun Petrochemical Research Institute, asphalt in Shenli Refinery's triumph is refined oil Factory's catalytic cracked oil pulp is distilled, and is obtained>430 DEG C of slurry oil S1.

>420 DEG C of slurry oil is heated to 150 DEG C and is maintained at 150 ± 5 DEG C, addition 4%（Account for slurry oil weight）Water content is 4.5% Asphalt in Shenli Refinery's FCC gasoline cut alkaline residue and lauryl amine 0.4%（Dodecyl primary amine, Jinan Jia Yu Chemical Co., Ltd.s）, stir Mix 45 minutes, obtain being modified slurry oil ARS-1.30% ARS-1 is added to 145 DEG C of Tahe residual oil（The 1/10mm of needle penetration 40） In, stir 45 minutes, obtain reconciling pitch, the property of pitch of reconciling is shown in Table 1.

Embodiment 2

The true boiling point distillation devices of FY- III produced using Fushun Petrochemical Research Institute, to Jingmen Company catalytic cracking Slurry oil is distilled, and is obtained>420 DEG C of slurry oil S2.

>420 DEG C of slurry oil is heated to 130 DEG C and is maintained at 130 ± 5 DEG C, addition 6%（Account for slurry oil weight）Jingmen catalysis split Change gasoline fraction alkaline residue（Water content 3.7%）With 0.8% palmitamide（Cetyl primary amine, the far grand limited public affairs of industry share in Changzhou Department）, stir 30 minutes, obtain being modified slurry oil ARS-2.40% ARS-2 is added to 145 DEG C of Jingmen solution-off pitch（Pin enters Spend 15 1/10mm）In, stir 30 minutes, obtain reconciling pitch, the property of pitch of reconciling is shown in Table 1.

Embodiment 3

The true boiling point distillation devices of FY- III produced using Fushun Petrochemical Research Institute, to SINOPEC Jiujiang Company catalytic cracking Slurry oil is distilled, and is obtained>420 DEG C of slurry oil S3.

>420 DEG C of slurry oil is heated to 130 DEG C and is maintained at 130 ± 5 DEG C, addition 8%（Account for slurry oil weight）SINOPEC Jiujiang Company Gasoline alkaline residue（Water content 2.1%）With 1.2% octadecyl primary amine（Jinan Jia Yu Chemical Co., Ltd.s）, stir 60 minutes, obtain Modified slurry oil ARS-3.10% ARS-3 is added in 145 DEG C No. 60 pitches of Tahe（The 1/10mm of needle penetration 55）In, stirring 30 minutes, obtain reconciling pitch, the property of pitch of reconciling is shown in Table 1.

Comparative example 1

Slurry oil is modified without gasoline alkaline residue, and with embodiment 1, the property of pitch of reconciling is shown in Table 1 for remaining.

Comparative example 2

Slurry oil is modified without gasoline alkaline residue, and with embodiment 2, the property of pitch of reconciling is shown in Table 1 for remaining.

Comparative example 3

Slurry oil is modified without gasoline alkaline residue, and with embodiment 3, the property of pitch of reconciling is shown in Table 1 for remaining.

The property of the mediation pitch of table 1.

From table 1, gasoline alkaline residue is modified the penetration ratio that slurry oil significantly improves mediation pitch with residual oil mediation.

Claims

1. a kind of preparation method of mediation pitch, it is characterised in that including following content：（1）Gasoline alkaline residue, aminated compounds add Enter and blending and modifying is heated into slurry oil, obtain being modified slurry oil；（2）Modified slurry oil is added in the asphalt stock of molten state and carried out Reconcile, obtain slurry oil mediation pitch.

2. in accordance with the method for claim 1, it is characterised in that：Described gasoline alkaline residue is constant pressure gasoline cut, FCC gasoline The alkali cleaning of cut refines the mixture of one or both of alkaline residue.

3. according to the method described in claim 1 or 2, it is characterised in that：Described gasoline alkaline residue is using preceding carrying out at dehydration Reason, the water content of gasoline alkaline residue is less than 10wt% after dehydration.

4. in accordance with the method for claim 1, it is characterised in that：Described aminated compounds is aromatic amine, fatty amine and more One or more in ethylene polyamine.

5. according to the method described in claim 1 or 4, it is characterised in that：Described aminated compounds is C₁₂~C₁₈Fatty amine in One or more.

6. in accordance with the method for claim 1, it is characterised in that：Described slurry oil is distillate catalytic cracked oil pulp, heavy oil Cracking slurry oil, RFCC slurry oil or distillate is urged to mix the one or more in refining RFCC slurry oil.

7. according to the method described in claim 1 or 6, it is characterised in that：Described slurry oil carries out plug processing, plug processing The boiling range scope of slurry oil afterwards>400℃.

8. in accordance with the method for claim 1, it is characterised in that：Described asphalt stock is road asphalt, residual oil and de-oiling The one or more of pitch.

9. in accordance with the method for claim 1, it is characterised in that：Gasoline alkaline residue addition accounts for the 0.5% ~ 12% of slurry oil weight.

10. in accordance with the method for claim 1, it is characterised in that：Aminated compounds addition account for slurry oil weight 0.05% ~ 5%。

11. in accordance with the method for claim 1, it is characterised in that：To reconcile on the basis of pitch gross mass, the tune of modified slurry oil It is 5% ~ 40% with ratio.

12. in accordance with the method for claim 1, it is characterised in that：Step（1）In obtained modification slurry oil first pass through at plug Reason, then carries out step again（2）Pitch harmonic process；Wherein being modified the boiling range scope after slurry topping processing is>400℃.

13. in accordance with the method for claim 1, it is characterised in that：Step（1）Hybrid reaction temperature be 70~160 DEG C, instead It is 10~120 minutes between seasonable.

14. in accordance with the method for claim 1, it is characterised in that：Step（2）Mediation temperature be 130 ~ 160 DEG C, during mediation Between be 10~120 minutes.