阅读说明：本技术 对苯乙烯重馏分油进行综合利用的装置和方法 (The device and method that styrene heavy distillate is comprehensively utilized ) 是由 孙浩 陈刚 简建超 张罗庚 张�成 冯海春 王寿璋 冯文远 常培廷 肖梅 张苡源 于 2019-09-30 设计创作，主要内容包括：本发明属于苯乙烯焦油回收再利用技术领域,涉及对苯乙烯重馏分油进行综合利用的装置和方法。本发明的装置,包括苯乙烯装置精馏塔、苯乙烯重馏分油储罐、提升管反应器和催化裂化装置分馏塔,苯乙烯装置精馏塔底部通过苯乙烯装置精馏塔塔底重馏分管线与苯乙烯重馏分油储罐相连通,苯乙烯重馏分油储罐通过跨线与提升管反应器相连通,提升管反应器顶部通过提升管反应器出口油气管线与催化裂化装置分馏塔相连通。本发明的综合利用方法使苯乙烯重馏分油与催化裂化装置的催化剂进行接触并发生反应,大部分转化为高价值的催化汽油、柴油和液化气等产品,同时副产少量干气和焦炭,实现高价值和环保加工利用苯乙烯重馏分油的目的。(The invention belongs to styrene tar recovery and reuse technology fields, are related to the device and method comprehensively utilized to styrene heavy distillate.The device of the invention, including styrene device rectifying column, styrene heavy distillate storage tank, riser reactor and catalytic cracking unit fractionating column, styrene device rectifier bottoms are connected by styrene device rectifying tower bottom heavy distillat pipeline with styrene heavy distillate storage tank, styrene heavy distillate storage tank is connected by cross-line with riser reactor, is exported oil-gas pipeline by riser reactor at the top of riser reactor and is connected with catalytic cracking unit fractionating column.Method of comprehensive utilization of the invention makes styrene heavy distillate be contacted and be reacted with the catalyst of catalytic cracking unit, it is largely converted into the products such as the catalytic gasoline, diesel oil and liquefied gas of high value, the a small amount of dry gas of by-product and coke simultaneously realize the purpose of high value and environmentally friendly processing and utilization styrene heavy distillate.)

1. the device that a kind of pair of styrene heavy distillate is comprehensively utilized, which is characterized in that including styrene device rectifying column (1), styrene heavy distillate storage tank (4), riser reactor (6) and catalytic cracking unit fractionating column (9), styrene device essence Tower (1) bottom is evaporated to be connected by styrene device rectifying tower bottom heavy distillat pipeline (3) with styrene heavy distillate storage tank (4) Logical, styrene heavy distillate storage tank (4) is connected by cross-line (13) with riser reactor (6), riser reactor (6) top Portion is connected by riser reactor outlet oil-gas pipeline (8) with catalytic cracking unit fractionating column (9).

2. the device according to claim 1 comprehensively utilized to styrene heavy distillate, which is characterized in that it is described across Line (13) is connected with the catalyst haptoreaction section of the middle part of riser reactor (6) or bottom.

3. the device according to claim 1 comprehensively utilized to styrene heavy distillate, which is characterized in that it is described across Flow control valve (14) are provided on line (13).

4. a kind of method that styrene heavy distillate is comprehensively utilized using claims 1 to 3 described in any item devices, Characterized by comprising the following steps:

(1) storage temperature of styrene heavy distillate storage tank is adjusted；

(2) styrene heavy distillate is controlled by flow control valve and enters riser reactor through cross-line, in riser reactor In, styrene heavy distillate mixes in proportion with catalytic cracking unit raw material, contacts simultaneously with the catalyst in riser reactor It reacts；

(3) oil gas that styrene heavy distillate catalysis reaction generates enters fractionating column together with the reaction oil gas of catalytic unit raw material Carry out later separation.

5. the method according to claim 4 comprehensively utilized to styrene heavy distillate, which is characterized in that the benzene Ethylene heavy distillate refers to that carrying out catalysis reaction in benzene and ethylene generates ethylbenzene and ethylbenzene progress catalytic dehydrogenating reaction generation benzene In the technical process of ethylene, pass through the heavy distillat of rectifying generation.

6. the method according to claim 5 comprehensively utilized to styrene heavy distillate, which is characterized in that the benzene The property of ethylene heavy distillate is that 20 DEG C of density are 900kg/m³-1100kg/m³, aromatic hydrocarbons weight content be 90%-100%, 20 DEG C Viscosity is 8.0mm²/s-12.0mm²/s。

7. the method according to claim 5 comprehensively utilized to styrene heavy distillate, which is characterized in that described to urge Agent includes molecular sieve, matrix, binder, in catalyst compound composition include aluminium oxide, silica, rare earth element and Phosphorus, wherein without alumina content >=42% in regenerated fresh catalyst, silica content >=40%, micro- index living >= 67, specific surface area >=180m²/ g, pore volume >=0.30ml/g.

8. the method according to claim 7 comprehensively utilized to styrene heavy distillate, which is characterized in that pass through tune Whole fresh catalyst is added to the replacement rate of catalytic cracking unit reaction-regeneration system, in control riser reactor with styrene weight Micro- index living of the equilibrium catalyst of distillate contact is 52-65, specific surface area >=110m²/ g, pore volume >=0.28ml/g.

9. the method according to claim 6 comprehensively utilized to styrene heavy distillate, which is characterized in that the step Suddenly the amount for entering the styrene heavy distillate of riser reactor in (2) accounts for the 0.8%-5% of riser combined feed weight ratio.

10. the method according to claim 6 comprehensively utilized to styrene heavy distillate, which is characterized in that described The storage temperature of styrene heavy distillate storage tank is 75 DEG C -120 DEG C in step (1), and step (2) described riser reactor goes out Mouth temperature is 490 DEG C -535 DEG C, pressure 150kPa-350kPa.

Technical field

The invention belongs to styrene tar recovery and reuse technology field, it is related to carrying out styrene heavy distillate comprehensive benefit Device and method.

Background technique

The production process of styrene product mainly includes two-stage process, is that benzene and ethylene carry out catalysis reaction and generates second first Benzene, then ethylbenzene carries out catalytic dehydrogenating reaction and generates styrene, part heavy distillat can be generated in product distillation process, also referred to as Styrene tar, yield are about the 2%-5% of styrene product amount.The component of this heavy distillate is more complicated, by styrene, The groups such as two polystyrene, alkylbenzene, hexichol isopropyl alkane, stilbenes, condensed-nuclei aromatics and a small amount of polymerization inhibitor are grouped as, and are held Polymerization reaction easily occurs and forms gel or solid at low temperature.

For the styrene heavy distillate of generation, conventional processing method is the fuel progress as heating furnace for petroleum chemical enterprise Burning or factory give down-stream enterprise's further processing to handle.If heavy distillate, as fuel combustion, is easy to cause into heating furnace The amount of nitrogen oxides that heating furnace discharges in flue gas is exceeded, is unsatisfactory for increasingly stringent environmental protection index requirement, and be easy to happen fire The problem of mouth frequent coking and blocking；If heavy distillate dispatches from the factory, then as new edition " National Hazard waste register " (2016) is by benzene Ethylene heavy distillate is included in hazardous waste, it is necessary to entrust qualified processed in units, and need to spend certain disposal costs, limit The factory disposition of styrene heavy distillate is made.Therefore a kind of more environmentally-friendly and economic method is needed to handle styrene double distilled Divide oil.

For example, Chinese invention patent 201710140150.6, which discloses a kind of styrene tar recycling and reusing, prepares sulfonic acid The method of salt, sulfonating agent is added into styrene tar, and styrene tar is converted to styrene tar sulphur by sulfonating reaction Hydrochlorate.The sulfonating reactions conditions such as molar ratio, reaction time, reaction temperature by control sulfonating agent and styrene tar, control The sulfonation degree of styrene tar improves its sulfonate yield.Styrene tar sulfonate contains sulfonic acid group, has hydrophily, It can be used as the surfactants such as cement water reducing agent.For petroleum chemical enterprise, the disadvantage is that newly-built sulfonation reaction device is needed, Technical process control is complicated, while styrene tar is converted into cheap cement water reducing agent, and economic benefit significantly drops It is low.

For example, Chinese invention patent 201520022544.8 discloses a kind of device for improving styrene yield in tar, Equipped with three line processes, a line process is to enter tar in luwa evaporator by extraction tower tar pipeline；Two wires process is Tar in styrene treating column is entered in luwa evaporator by treating column tar pipeline；Three line processes are when tar viscosity increases The C9 flux oil of added-time, C9 dilution oil tank are entered in luwa evaporator by pipeline, and three line processes are finally pooled to wiped film vaporization In device, steam is entered in luwa evaporator by steam pipe line to tar heating, and tar has two after heating in luwa evaporator Kind state, one is gaseous state styrene by the discharge recycling of styrene gas pipeline, and one is tar to be drawn to tar by gear pump In tank.By becoming gaseous state in tar emission to luwa evaporator, the styrene in tar heats in luwa evaporator, lead to The recycling of styrene gas pipeline is crossed, reduces waste, reduces production cost.The shortcomings that the method is can only to recycle content in tar The styrenic component of 5%-8% is accounted for, the tar component of 90% or more residue is further processed there is still a need for suitable approach.

Summary of the invention

It is an object of the invention to overcome drawbacks described above existing for existing production technology, propose to styrene heavy distillate The device comprehensively utilized additionally provides the method for utilizing styrene heavy distillate using the device, makes styrene heavy distillat Oil is contacted and is reacted with the catalyst of catalytic cracking unit, and catalytic gasoline, the diesel oil of high value are largely converted into With the products such as liquefied gas, while a small amount of dry gas of by-product and coke realize high value and environmentally friendly processing and utilization styrene heavy distillate Purpose.

The present invention, which is that the following technical solution is employed, to be realized:

The present invention provides the devices that a kind of pair of styrene heavy distillate is comprehensively utilized, including styrene device rectifying Tower, styrene heavy distillate storage tank, riser reactor and catalytic cracking unit fractionating column, styrene device rectifier bottoms are logical It crosses styrene device rectifying tower bottom heavy distillat pipeline to be connected with styrene heavy distillate storage tank, styrene heavy distillate storage tank It is connected by cross-line with riser reactor, exports oil-gas pipeline by riser reactor at the top of riser reactor and urge Change cracking unit fractionating column to be connected.

Further, the cross-line is connected with the catalyst haptoreaction section of the middle part of riser reactor or bottom.

Further, flow control valve is provided on the cross-line.

The present invention also provides a kind of methods comprehensively utilized using above-mentioned apparatus to styrene heavy distillate, including Following steps:

(1) storage temperature of styrene heavy distillate storage tank is adjusted；

(2) styrene heavy distillate is controlled by flow control valve and enters riser reactor through cross-line, it is anti-in riser It answers in device, styrene heavy distillate mixes in proportion with catalytic cracking unit raw material, connects with the catalyst in riser reactor It touches and reacts；

(3) oil gas that styrene heavy distillate catalysis reaction generates enters together with the reaction oil gas of catalytic unit raw material divides It evaporates tower and carries out later separation.

Specifically, the styrene heavy distillate refers to that carrying out catalysis reaction in benzene and ethylene generates ethylbenzene and ethylbenzene It carries out catalytic dehydrogenating reaction to generate in the technical process of styrene, the heavy distillat generated by rectifying.

Wherein, it is 900kg/m that the property of the styrene heavy distillate, which is 20 DEG C of density,³-1100kg/m³, aromatic hydrocarbons weight contains Amount is 90%-100%, and 20 DEG C of viscositys are 8.0mm²/s-12.0mm²/s。

Wherein, the catalyst includes molecular sieve, matrix, binder, and compound composition includes aluminium oxide, oxygen in catalyst SiClx, rare earth element and phosphorus, wherein without alumina content >=42% in regenerated fresh catalyst, silica content >=40%, micro- index >=67 living, specific surface area >=180m²/ g, pore volume >=0.30ml/g.

Specifically, being added to the replacement rate of catalytic cracking unit reaction-regeneration system by adjusting fresh catalyst, control is mentioned Micro- index living of the equilibrium catalyst contacted in riser reactors with styrene heavy distillate is 52-65, specific surface area >= 110m²/ g, pore volume >=0.28ml/g.

Specifically, the step (2) in enter riser reactor styrene heavy distillate amount account for riser always into Expect the 0.8%-5% of weight ratio.

Specifically, the storage temperature of styrene heavy distillate storage tank is 75 DEG C -120 DEG C in the step (1), step (2) The outlet temperature of the riser reactor is 490 DEG C -535 DEG C, pressure 150kPa-350kPa.

In the present invention, the reaction that styrene heavy distillate mainly occurs under the effect of the catalyst includes aromatic side chain cracking It is changed into the aromatic hydrocarbons of low-carbon alkene and smaller side chain, transalkylation occurs, dehydrogenative condensation reaction is changed into polycyclic aromatic hydrocarbon and coke Deng.

The beneficial effects of the present invention are:

(1) method of comprehensive utilization of the invention is relied on the existing processing flow of petroleum chemical enterprise, is not being needed to each process units Carry out it is larger it is dynamic change in the case where, styrene heavy distillate is used as to the charging of FCC riser, realization The purpose of high value and environmentally friendly processing and utilization styrene heavy distillate；

(2) styrene heavy distillate is contacted and is reacted with high-temperature catalytic Cracking catalyst, in the product of generation 85% the above are liquid products such as the catalytic gasoline of high value, diesel oil and liquefied gas, remaining as a small amount of dry gas and coke, improve Its economic use value；

(3) styrene heavy distillate is not re-used as the fuel combustion of heating furnace, to avoid heating furnace because of the styrene that burns The problem of amount of nitrogen oxides that heavy distillate leads to discharge in flue gas is unsatisfactory for environmental protection index requirement generation；

(4) styrene heavy distillate is not re-used as hazardous waste factory, and waste of not causing danger entrusts disposal costs；

Performance analysis:

Specific benefit calculation is as follows:

When fuel combustion of the styrene heavy distillate as heating furnace, price is about 2000 yuan/ton；And work as styrene When heavy distillate is by catalysis reaction, 85% or more is converted into the liquid products such as catalytic gasoline, diesel oil and liquefied gas, and price is about 7200 yuan/ton, remaining is 15% for dry gas and coke etc., and price is about 2000 yuan/ton, at this time styrene heavy distillate reaction product Average price be 85%*7200+15%*2000=6420 yuan/ton.Therefore, styrene heavy distillate is after catalysis reaction Price is compared with as furnace fuel, and price increase 6420-2000=4420 yuan/ton.

By taking the styrene device of 8.5 ten thousand tons/year of scales as an example, heavy distillate yield is based on the 3% of styrene product yield It calculates, can produce 2550 tons of styrene heavy distillate every year.This part styrene heavy distillate is through catalysis reaction and as heating furnace Fuel is compared, and can increase benefit every year is ten thousand yuan of 2550*4420=1127.10.

The processing charges such as the energy consumed when processing styrene heavy distillate in view of catalytic unit are 80 yuan/ton, every year Need to increase by ten thousand yuan of processing cost 80*2550=20.4.

After deducting processing cost, producible economic benefit is=ten thousand yuan/year of 1127.10-20.4=1106.7.

Detailed description of the invention

Attached drawing is used to provide further understanding of the present invention, and constitutes part of specification, with reality of the invention It applies example to be used to explain the present invention together, not be construed as limiting the invention.

In the accompanying drawings:

Fig. 1 is the flow diagram of embodiment 1；

Fig. 2 is the flow diagram of comparative example 1；

It is respectively marked in figure as follows: 1 styrene device rectifying column, 2 styrene product pipelines, 3 styrene device rectifying towers Bottom heavy distillat pipeline, 4 styrene heavy distillate storage tanks, 5 styrene heavy distillates factory pipeline, 6 riser reactors, 7 are promoted Pipe reactor feeding line, 8 riser reactors export oil-gas pipeline, 9 catalytic cracking unit fractionating columns, 10 catalytic cracking units Liquid product pipeline, 11 catalytic cracking unit dry gas product pipelines, 12 riser reactor stripping sections, 13 cross-lines, 14 flow controls Valve processed.

Specific embodiment

In order to which the object of the invention, technical solution is more clearly understood, with reference to the accompanying drawing, the present invention is made further detailed It describes in detail bright.Experimental method described in following embodiments is unless otherwise specified conventional method；It is not specified in embodiment specific Technology or conditions person described technology or conditions or carries out according to the literature in the art according to product description；It is described Reagent and material commercially obtain unless otherwise specified.

Capital equipment: FCC riser is MIP-CGP series connection riser reactor, and catalytic cracking is former Material plus hydrogen wax oil.

As shown in Figure 1,1 bottom of styrene device rectifying column by styrene device rectifying tower bottom heavy distillat pipeline 3 with Styrene heavy distillate storage tank 4 is connected, and styrene heavy distillate storage tank is connected by cross-line 13 with riser reactor 6, Oil-gas pipeline 8 is exported by riser reactor at the top of riser reactor to be connected with catalytic cracking unit fractionating column 9.

The interface of cross-line connection riser reactor is provided with the spray head of four groups of stainless steel materials.The minimum nominal of spray head Pressure is 5.0MPa.

Styrene device rectifying column top products send out styrene device rectifying column, bottom by styrene product pipeline 2 Product is sent to styrene heavy distillate storage tank by styrene device rectifying tower bottom heavy distillat pipeline and is stored, the heavy distillat of storage It is oily that loading system factory is periodically delivered to by styrene heavy distillate factory pipeline 5 or is burnt as furnace fuel.

Catalytic cracking unit raw material by riser reactor feeding line 7 enter riser reactor bottom into Expect sections of atomization, in riser reactor, catalytic cracking unit raw material contacts with catalyst and occur series reaction, reaction life At oil gas oil-gas pipeline exported by the riser reactor on top enter catalytic cracking unit fractionating column and further separate, point The liquid products such as the catalytic liquefaction gas, catalytic gasoline, the catalytic diesel oil that separate out are sent by catalytic cracking unit liquid product pipeline 10 Device out, the dry gas product isolated pass through 11 carrying device of catalytic cracking unit dry gas product pipeline of tower top.Riser is anti- Answer catalytic cracking unit coke product in device stripping section 12 to be attached to catalyst surface, enter together with catalyst regenerative system into Row is burnt.

Meanwhile increasing the cross-line of styrene heavy distillate storage tank to FCC riser, by benzene Ethylene heavy distillate is introduced into the middle part of FCC riser or the catalyst haptoreaction section of bottom, across Setting flow control valve 14 on line.Mass flowmenter is installed on cross-line.Flow control valve and riser bottom feed line Control valve is set as chain control.It is means commonly used in the prior art that flow control valve, which controls material conveying in cross-line,.

The minimum nominal pressure of flow control valve is 5.0MPa.

The material of flow control valve is carbon steel.Pipeline material of the cross-line between flow control valve and riser reactor For stainless steel, the pipeline material between flow control valve and styrene heavy distillate storage-tank effluent line is carbon steel.

It is now that raw material involved in present embodiment and preparation condition parameter Unify legislation is as follows to avoid repeating, It is repeated no more in specific embodiment:

Styrene heavy distillate refers to that carrying out catalysis reaction in benzene and ethylene generates ethylbenzene and ethylbenzene progress catalytic dehydrogenation Reaction generates in the technical process of styrene, the heavy distillat generated by rectifying.The property of styrene heavy distillate is 20 DEG C close Degree is 900kg/m³-1100kg/m³, aromatic hydrocarbons weight content is 90%-100%, and 20 DEG C of viscositys are 8.0mm²/s-12.0mm²/s。

Catalyst includes molecular sieve, matrix, binder, and compound composition includes aluminium oxide, silica, rare earth in catalyst Element and phosphorus, wherein silica content >=40% is micro- without alumina content >=42% in regenerated fresh catalyst Index >=67 living, specific surface area >=180m²/ g, pore volume >=0.30ml/g.The catalyst that the following example uses is HCGP-2 Catalytic cracking catalyst.

The replacement rate of catalytic cracking unit reaction-regeneration system is added to by adjusting fresh catalyst, control promotes tube reaction Micro- index living of the equilibrium catalyst contacted in device with styrene heavy distillate is 52-65, specific surface area >=110m²/ g, hole body Product >=0.28ml/g.

(1) storage temperature for adjusting styrene heavy distillate storage tank is 75 DEG C -120 DEG C；

(2) styrene heavy distillate is controlled by flow control valve and enters riser reactor through cross-line, it is anti-in riser It answers in device, styrene heavy distillate is mixed with catalytic cracking unit raw material, and the amount of styrene heavy distillate accounts for riser combined feed The 0.8%-5% of weight ratio；It contacts and reacts with catalyst in riser reactor；The outlet of riser reactor Temperature is 490 DEG C -535 DEG C, pressure 150kPa-350kPa；Styrene heavy distillate mainly occurs under the effect of the catalyst Reaction include that aromatic side chain cracking is changed into the aromatic hydrocarbons of low-carbon alkene and smaller side chain, it is anti-that transalkylation, dehydrogenative condensation occurs Polycyclic aromatic hydrocarbon and coke etc. should be changed into；

(3) oil gas that styrene heavy distillate catalysis reaction generates enters together with the reaction oil gas of catalytic unit raw material divides It evaporates tower and carries out later separation.