CN106675613B

CN106675613B - A kind of processing method of phenol tar

Info

Publication number: CN106675613B
Application number: CN201510750991.XA
Authority: CN
Inventors: 初人庆; 李晓姝; 郭丹; 刘继华; 乔凯; 勾连忠
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: 2015-11-09
Filing date: 2015-11-09
Publication date: 2018-06-19
Anticipated expiration: 2035-11-09
Also published as: CN106675613A

Abstract

The present invention discloses a kind of processing method of phenol tar, including entering coke drum after the heated stove heat of conventional coking raw material, when fill that burnt amount reaches coke drum maximum and fill burnt height in coke drum 80% 100%, it is preferred that 90% 95% when, stops conventional coking raw material and fills coke, switching phenol tar continues to fill coke through coke drum steam blowing pipeline, when temperature is less than 300 400 DEG C in coke drum, it is preferred that 350 400 DEG C, more preferable 380 400 DEG C stop phenol tar and fill burnt progress steam purging process, coking gas, which enters after fractionating column is fractionated into, obtains naphtha, diesel oil, wax oil fraction, coke is obtained in coking tower.This method can improve phenol tar added value of product.

Description

A kind of processing method of phenol tar

Technical field

The present invention relates to a kind of processing methods of phenol tar.

Background technology

For synthesizing phenol generally using cumene method, i.e. isopropylbenzene generates oxidation isopropylbenzene, peroxidating through air oxidation at present Further phenol and acetone, and a certain number of solid waste of by-product are resolved into acidification to isopropylbenzene --- and " containing phenolic tar ".By Containing a large amount of toxic volatile components in containing phenolic tar, serious air pollution can be led to by burning in open environment, Therefore, it is difficult to regard fuel to carry out heat recovery.For the needs of environmental protection, phenolic tar generally needs in normal productive process Burning disposal is carried out using special incinerator.It in this case, both can not be to containing a large amount of high added values contained in phenolic tar Product is recycled, and must increase investment in terms of solid waste processing, therefore and have no commercial value, as can to phenolic tar Depth reprocessing is carried out, high value added product is obtained simultaneously, can undoubtedly reduce the production cost of phenol.

Chinese patent CN201210117682.5 discloses a kind of method that phenol, acetophenone are recycled from phenol tar, Sulfate is added in phenolic tar as catalyst, while adds in a kind of high-temperature solvent oil, temperature is first increased to by agitating and heating 240-260 DEG C maintains a period of time, then temperature is increased to 300-360 DEG C of progress cracking reaction, obtains containing phenol, acetophenone Wait useful constituents substance.But the patent is not described further final residue place to go, is only capable of being burnt as waste Burning processing.

Delayed coking unit as oil plant secondary operation device have its unique advantage, to raw material it is adaptable, can Raise productivity and improve the quality diesel oil, improves diesel and gasoline ratio.Delayed coking unit can have been handled including straight run at present（Visbreaking is hydrocracked）Residual oil, Recycle oil, Tar sands, pitch, depitching tar, clarified oil and coal derivative, catalytic cracked oil pulp, refinery's sump oil（Mud） Raw material is planted Deng more than 60, the Kang Si carbon residues that processing raw material has can be 3.8%-45% or more, and delayed coking unit is light due to having The features such as matter oil yield is high, investment cost is low is always the important manufacturing process of world's heavy oil lighting.

In delayed coking unit heat exchange process domestic newly-built at present, coking raw material successively respectively with coking main fractionating tower side Line is light, weight wax tailings heat exchange, and temperature is 280-300 DEG C after heat exchange, subsequently into the breeze way of coking main fractionating tower bottom, Bottom of towe is mixed with recycle oil, and temperature is 340-355 DEG C, then is pumped into heating furnace with furnace charge.Fresh feed and recycle oil Mixed oil plant is rapidly heated to required heater outlet temperature by heating furnace（500-505℃）, enter green coke through switching valve In coke drum high temperature oil gas heat cracking reaction, high-temperature liquid-phase generation thermal cracking and condensation reaction occur for coke drum bottom, until raw Until hydrocarbon vapours and coke.It is fed in the prior art using phenol tar as delayed coking, has no that pertinent literature is reported.

Invention content

In view of the deficiencies of the prior art, it is an object of the invention to solve phenol products in phenol tar to be difficult to recycle, and And phenol tar is only capable of the problem of resource waste generated as solid waste progress burning disposal, improves added value of product.

A kind of processing method of phenol tar including entering coke drum after the heated stove heat of conventional coking raw material, works as coke Burnt amount is filled in charcoal tower reach and stop conventional coking raw material when coke drum maximum fills the 80%-100%, preferably 90%-95% of burnt height and fill Coke, switching phenol tar continue to fill coke through coke drum steam blowing pipeline, are less than 300-400 DEG C when warm in coke drum, preferably 350-400 DEG C, more preferable 380-400 DEG C stops phenol tar and fills burnt progress steam purging process, and coking gas enters fractionating column Naphtha, diesel oil, wax oil fraction are obtained after being fractionated into, coke is obtained in coking tower.

In the above method, the routine coking raw material includes decompression residuum, reduced crude, heavy crude, decompressed wax oil, takes off Oil asphalt, residual hydrogenation heavy oil, thermal cracking residue, the tapped oil of lube oil finishing, catalytic cracking recycle oil and clarified oil, ethylene One or more of pyrolysis residue and tar asphalt etc..

In the above method, the phenol tar can be the techniques benzene such as cumene method, toluol-benzene formic acid method, sulfonation method One or more of phenol tar that phenol generates.

In the above method, the control of furnace outlet temperature is 465-530 DEG C, preferably 485-510 DEG C, more preferable 495-505 ℃。

In the above method, the feeding temperature of the phenol tar is 150-300 DEG C, preferably 200-300 DEG C, more preferable 250 ℃-300℃。

In the above method, stop coke drum phenol tar and fill burnt steam purging process, preferably save that vapor is small to blow over Journey directly carries out vapor and blows greatly, blows time 0.5-5h, preferably 0.5-2h greatly.

Polymerisation easily occurs after phenol tar heating can not be as conventional coking raw material.The method of the present invention can Phenol tar is made to be fully converted to coke and distillate, phenol tar is made to turn waste into wealth, improves the utilization rate of phenol tar, together When, high-temperature vapor dosage is reduced, coked waste water discharge is reduced simultaneously, reduces energy expenditure.

Specific embodiment

Method is further illustrated the present invention, but following embodiment is not formed to the present invention with reference to embodiment and comparative example Limitation.

Embodiment 1

Raw material is used selected from certain refinery's phenol tar, and specific nature is shown in Table 1.Conventional coker feedstock depressurizes slag for certain refinery Oil, furnace outlet temperature are 500 DEG C, when the burnt amount of filling of decompression residuum STRENGTH ON COKE tower reaches maximum safety and fills burnt height 90%, are stopped Only decompression residuum STRENGTH ON COKE tower fills coke, is switched to 250 DEG C of phenol tar and continues STRENGTH ON COKE by coke drum steam blowing pipeline Tower fills coke, when temperature is less than 400 DEG C in coke drum, stops phenol tar and fills burnt process, it is total that final phenol tar amount accounts for coking Inlet amount 10%, vapor blow greatly time 3.5h, and specific product distribution is shown in Table 2.

Comparative example 1

For the ease of comparing beneficial effects of the present invention, using the decompression residuum of embodiment 1 as the Conventional delayed coking of raw material Experiment is as blank test, and other experimental conditions are identical with embodiment 1, and product distribution is shown in Table 2, finally converses equivalent 10% phenol tar product is distributed.

Embodiment 2

Conventional coker feedstock furnace outlet temperature is 510 DEG C, when the burnt amount of filling of decompression residuum STRENGTH ON COKE tower reaches maximum Safety fills burnt height 95%, stops decompression residuum STRENGTH ON COKE tower and fills coke, is switched to 280 DEG C of phenol tar and passes through coke drum steam Blow line continues STRENGTH ON COKE tower and continues to fill coke, when temperature is less than 420 DEG C in coke drum, stops phenol tar and fills burnt process, Final phenol tar amount accounts for coking total feed 20%, and vapor is small to blow time 1h, blows time 3h greatly, and specific product distribution is shown in Table 3。

Comparative example 2

Using the phenol tar of embodiment 2, decompression residuum as raw material, 20% phenol tar of refining is mixed using Conventional delayed coking, i.e., Phenol tar is mixed different substances together in decompression residuum, is fractionated into bottom of towe heat exchange, heating furnace is heated to 495 DEG C and enters coke drum, Qi Tashi It is identical with embodiment 2 to test condition, experiment carries out 40h aftercuts bottom of towe and heating furnace tube coking is serious, and device is forced to stop Work is overhauled, and seriously affects coking plant on-stream time, and the product distribution of acquisition is shown in Table 3.

As can be seen from the above embodiments, it using the processing method of phenol tar provided by the invention, does not cause to heat Furnace coking seriously affects coking on-stream time, meanwhile, phenol tar is converted into high value added product naphtha and diesel oil, and generates A small amount of gas, wax oil and coke efficiently solve phenol tar and are only capable of carrying out burning disposal as solid waste and generating Problem of resource waste.

1 phenol tar test data of table

α：α-methylstyrene；AP：Acetophenone；DMBA：Dimethyl benzyl alcohol；α-dimer：The dimerization of α-methylstyrene Body；CP：Withered phenol

2 product of table is distributed

* embodiment 1 is to be calculated using residual oil and phenol tar charging summation as 100%.

3 product of table is distributed

Claims

1. a kind of processing method of phenol tar, it is characterised in that：Including entering coke after the heated stove heat of conventional coking raw material Charcoal tower stops conventional coking raw material and fills coke, cuts when filling burnt amount in coke drum and reaching when coke drum maximum fills the 80%-95% of burnt height It changes phenol tar to continue to fill coke through coke drum steam blowing pipeline, when less than 420 DEG C stopping phenol tars of temperature fill coke in coke drum Steam purging process is carried out, coking gas, which enters after fractionating column is fractionated into, obtains naphtha, diesel oil, wax oil fraction, in coking tower Obtain coke；Wherein, the feeding temperature of the phenol tar is 150-300 DEG C；Stop coke drum phenol tar and fill burnt progress water Purge vapor process directly carries out vapor and blows greatly, blows time 0.5-5h greatly.

2. according to the method described in claim 1, it is characterized in that：Burnt height is filled when filling burnt amount in coke drum and reaching coke drum maximum Stop conventional coking raw material during the 90%-95% of degree and fill coke.

3. according to the method described in claim 1, it is characterized in that：The routine coking raw material includes decompression residuum, normal pressure slag Oil, heavy crude, decompressed wax oil, de-oiled asphalt, residual hydrogenation heavy oil, thermal cracking residue, the tapped oil of lube oil finishing, catalysis One or more of cracked cycle oil, catalytic cracking clarified oil, cracking of ethylene residual oil, tar asphalt.

4. according to the method described in claim 1, it is characterized in that：The phenol tar is cumene method, toluol-benzene formic acid One or more of phenol tar that method, sulfonation legal system phenol generate.

5. according to the method described in claim 1, it is characterized in that：The control of furnace outlet temperature is 465-530 DEG C.

6. according to the method described in claim 5, it is characterized in that：The control of furnace outlet temperature is 485-510 DEG C.

7. according to the method described in claim 6, it is characterized in that：The control of furnace outlet temperature is 495-505 DEG C.

8. according to the method described in claim 1, it is characterized in that：The feeding temperature of the phenol tar is 200-300 DEG C.

9. according to the method described in claim 1, it is characterized in that：The feeding temperature of the phenol tar is 250 DEG C -300 DEG C.