CN109851460A - Naphtha pyrolysis sequentially separates the method coupled with PDH technique - Google Patents
Naphtha pyrolysis sequentially separates the method coupled with PDH technique Download PDFInfo
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Abstract
The present invention relates to a kind of naphtha pyrolysises sequentially to separate the method coupled with PDH technique, mainly solves engineering construction investment height in the prior art, takes up a large area, the low problem of propene yield.The present invention sequentially separates the method coupled with PDH technique by using a kind of naphtha pyrolysis, leverages fully on sequence separation existing equipment, realizes that PDH product gas couples simultaneously propylene enhancing product with ethene cracking gas.For 80~1,200,000 tons/year of ethylene units and 600,000 tons/year of PDH devices, reduce equipment investment 3.18~4.89 hundred million yuan, it saves 1.8 hectares of area occupied of technical solution and preferably solves the above problem, can be used for during naphtha pyrolysis sequence separation couples with PDH technique.
Description
Technical field
The present invention relates to a kind of naphtha pyrolysises sequentially to separate the method coupled with PDH technique, is a kind of PDH technique and stone
The integrated technique of cerebrol cracking sequence separating technology coupling.Reactor product gas from PDH device relies on ethylene unit
Existing equipment is separated, and is only increased the produce load of part ethylene unit, is thus reduced equipment investment expense, reduce
Plant construction land used, and achieved the purpose that propylene enhancing product, it can be applied in the industrial production of ethylene unit.
Background technique
Ethylene industry is the faucet of petrochemical industry, and the development of ethylene technology is all paid much attention in countries in the world.Currently, global second
Alkene production capacity is huge, and China's ethylene production capacity increases year by year.Ethylene process technology is mainly by KBR, SW, ABB in the world
The advanced technologies of the patents quotient such as Lummus, TECHNIP exploitation, have and invest the spies such as low, less energy consumption, Recovery rate of ethylene height
Point.Ethylene mainly passes through the acquisition such as cracking naphtha and alkane, hydrogenated diesel oil, therefore pyrolysis furnace technology is the core of ethylene unit
The heart also determines the material balance of cracking product distribution and entire ethylene unit.Ethylene unit mainly includes cracking and separation two
A technical process, Technology for Ethylene Plant include: sequence separation process, front-end deethanization process, predepropanization process and gradual again
Separation process etc..Sequence isolation technics is separated according to the sequence of hydrocarbon molecules amount each in cracking gas from low to high, it may be assumed that is split
It vents one's spleen and is introduced into domethanizing column, isolate methane and hydrogen.Demethanation tower reactor contains two or more component of carbon two and carbon, is sent into de- second
Alkane tower.Deethanizer overhead send ethylene rectifying column after isolating the hydrogenated acetylene removal of C2 material, and dethanizer kettle liquid is sent to depropanization
Tower.Propylene rectification tower is sent after the hydrogenated acetylene removal of depropanization tower top C3 material, depropanizing tower kettle liquid is sent to debutanizing tower and carries out rectifying
Separation.
Propylene is a kind of important Organic Chemicals, and consumption figure is only second to ethylene.Using dehydrogenating propane PDH technology system third
Alkene propene yield with higher, and produced using the single raw material of propane, compared to other techniques, technical process compares
It is relatively simple.Currently, mature preparing propylene by dehydrogenating propane technique has: the Oleflex continuous moving bed process, ABB of Uop Inc.
Catofin circulation multiple reactor system process, the Star technique of Krupp Uhde company, the Linde-BASF of Lummus company are public
PDH technique of department etc..Wherein: most, the largest technique of application is Catofin technique and Oleflex technique, two kinds of techniques
The main distinction be dehydrogenation and catalyst regeneration part.
103087758 A of patent of invention CN in the prior art relates to a kind of naphtha industrial pyrolysis furnace Maximum Value
The Component for changing model, for optimizing the operation of naphtha industrial pyrolysis furnace, the petroleum chemicals for producing naphtha pyrolysis furnace are total
Value reaches maximum.105585399 A of patent of invention CN provides a kind of method that naphtha catalytic cracking produces propylene, overcomes
Prior art naphtha catalytic cracking produces the low problem of propene yield.105264050 A of patent of invention CN, which provides one kind, to be made
The method of the yield optimization and raising yield of light olefin and aromatics.108067228 A of patent of invention CN discloses one kind third
Alkane dehydrogenation and preparation method thereof, so that Propylene Selectivity reaches 90% or more, and with good stability.Invention is special
Sharp 107973682 A of CN provides a kind of method of preparing propylene by dehydrogenating propane, available higher conversion of propane and propylene
Selectivity.107954815 A of patent of invention CN relates to a kind of separation method of dehydrogenating propane reaction gas, has lower energy
Consumption and the hydrogen and propylene that high-purity can be obtained.
In the prior art, CN 107602324 A, CN 107602323 A, CN 107673947 A relate to PDH technique
With the coupling of ethylene process, but there is no be applied to ethylene unit sequence separation process in, there is not yet PDH technique and naphtha are split
The report of solution sequence separating technology coupling；And existing ethylene unit naphtha pyrolysis and PDH device traditional technology route there is
Engineering construction investment is high, takes up a large area, the low problem of propene yield.
Summary of the invention
The technical problem to be solved by the present invention is to the height of engineering construction investment in the prior art, take up a large area, and propylene is received
The low problem of rate provides the new naphtha pyrolysis of one kind and sequentially separates the method coupled with PDH technique, has engineering construction investment
Low, occupied area is small, the high advantage of propene yield.
To solve the above problems, The technical solution adopted by the invention is as follows: a kind of separation of naphtha pyrolysis sequence and PDH work
The method of skill coupling, the fresh propane charging external from battery limit (BL) is with the recycled propane from de-oiling column overhead and from propylene essence
After the recycled propane mixing for evaporating tower tower bottom, enter propane gasification tank jointly, tank bottom heavy constituent is removed de-oiling Tower System and is ultimately sent to
Reaction gas industrial furnace makees liquid supplement fuel, and tank deck light component is sent into PDH reactor, and propane carries out dehydrogenation reaction in the reactor
The product gas for being rich in propylene is generated, the product gas after reaction is sent into compression and the caustic wash unit of ethylene unit；Cracking stock stone brain
Oil enter pyrolysis furnace, in pyrolysis furnace occur cracking reaction generate include ethylene Pintsch process gas, cracking gas after chilling with
Reactor product gas from PDH device, which converges, is sent into ethylene unit compression and caustic wash unit, then successively through domethanizing column, de- second
Alkane tower, depropanizing tower, debutanizing tower are separated, and C2 group is distributed into ethylene rectifying column and carries out isolated ethylene product, C3 group
It is distributed into propylene rectification tower and carries out isolated propylene product.
In above-mentioned technical proposal, it is preferable that ethylene unit nominal capacity is 80~1,200,000 tons/year, product propylene/second
Alkene ratio is 0.52.
In above-mentioned technical proposal, it is preferable that PDH device nominal capacity is 600,000 tons/year, produces ethylene product 1.29 ten thousand
Ton/year, produce 51.90 ten thousand tons/year of propylene product.
In above-mentioned technical proposal, it is preferable that the operating condition of Furnace of Ethylene Cracking Plant are as follows: reaction pressure 0.10~
0.25MPaA, 810~870 DEG C of reaction temperature.
In above-mentioned technical proposal, it is preferable that the operating condition of PDH device reaction device are as follows: reaction pressure 0.10~
0.35MPaA, 500~700 DEG C of reaction temperature.
In above-mentioned technical proposal, it is preferable that propane gasification tank tank deck light component enters after preheating as reaction feed
Heating furnace is sent into PDH reactor after being heated to reaction temperature.
In above-mentioned technical proposal, it is preferable that propane gasification tank tank deck light component as reaction feed through being preheated to 180~
Enter after heating furnace is heated to reaction temperature after 260 DEG C and is sent into PDH reactor.
In above-mentioned technical proposal, it is preferable that it leverages fully on ethylene unit existing equipment and is separated, ethylene unit portion
Subset produce load is opposite to be improved, but the equipment that PDH device uses is reduced, and it is dry to eliminate product air compressor, product gas
Gas, dethanizer feed drier, dethanizer, cold box system, propylene rectification tower, propylene rectification tower feed desulfurization bed, ethylene
Refrigeration compressor, propylene refrigeration compressor.
The present invention relates to a kind of naphtha pyrolysises sequentially to separate the method coupled with PDH technique, and technology to be solved is asked
Topic is exactly that engineering construction investment existing for existing ethylene unit and dehydrogenating propane device traditional technology route is costly, occupied area
Greatly, the low problem of propene yield.A kind of technical side that new PDH technique is coupled with naphtha pyrolysis sequence separating technology is provided
Case is able to produce more propylene than naphtha pyrolysis using PDH technique, improves the yield of propylene product, and integration
Device has many advantages, such as that equipment investment is low, and occupied area is small, and economy is more preferably.The present invention relies on ethylene unit sequence separation process
Existing equipment only carries out capacity expansion revamping to part ethylene unit, realizes that PDH device reaction product gas and ethylene cracking gas are total
With isolated integrated technique, and achieve the purpose that propylene enhancing product.For 80~1,200,000 tons/year of ethylene units and
For 600000 tons/year of PDH devices, the method coupled with PDH technique is sequentially separated using naphtha pyrolysis of the present invention, reduces equipment
Investment cost 3.18~4.89 hundred million yuan, had both achieved preferable economic effect by about 1.8 hectares of Economization on land area occupied
Benefit, and achieve preferable technical effect.
Detailed description of the invention
Fig. 1 is the flow diagram of the method for the invention.
In Fig. 1:
Material: 01 --- cracking stock；31 --- methane and hydrogen；32 --- ethylene；33 --- propylene；34 --- C4 group
Point；35 --- drippolene；36 --- Pyrolysis fuel oil PFO；71 --- propane feed；
Device: 11 --- cracking unit；12 --- quenching unit；13 --- compression unit；21 --- domethanizing column；
22 --- dethanizer；23 --- ethylene rectifying column；24 --- depropanizing tower；25 --- propylene rectification tower；26 --- debutanization
Tower；81 --- PDH reaction member；82 --- PDH separative unit.
The present invention will be further described below by way of examples, but is not limited only to the present embodiment.
Specific embodiment
[comparative example 1]
The prior art separates ethylene unit by the sequence of cracking stock of naphtha, and nominal capacity is 800,000 tons/year.The dress
Setting ethylene yield is 80.00 ten thousand tons/year, and propylene yield is 41.60 ten thousand tons/year, and product propylene/ethylene ratio is 0.52.Consumption is former
278.64 ten thousand tons/year of work stone cerebrol.
For the prior art using fresh propane as the PDH device of raw material, nominal capacity is 600,000 tons/year.Ethylene yield 1.29
Ten thousand tons/year, 51.90 ten thousand tons/year of propylene yield, fresh propane consumes 62.93 ten thousand tons/year.
[embodiment 1]
A kind of naphtha pyrolysis sequentially separates the method coupled with PDH technique, as shown in Figure 1, PDH device: fresh propane
Raw material 71 and the recycled propane from de-oiling column overhead and the recycled propane from propylene rectification tower tower bottom enter propane jointly
Gasification tank gasifies, and the material after gasification enters heating furnace and reactor 81 occurs dehydrogenating propane and reacts, after PDH device reaction
Product gas and the cracking gas that generates of ethylene unit enter the compression unit 13 of ethylene unit jointly.
Ethylene unit: naphtha 01 is cracked into pyrolysis furnace 11 comprising ethylene first as the cracking stock of ethylene unit
Pintsch process gas, be sent to quenching unit 12.Cracking gas goes out drippolene 35 and cracking fuel through chilling, washing separation
Oil 36, the cracking gas after chilling, washing are increased into compression and caustic wash unit 13 jointly with the product gas from PDH device
Domethanizing column 21, which is sent to, after pressure, alkali cleaning, drying carries out later separation.
Demethanizer column overhead isolates methane and hydrogen, and tower reactor C2 and C2 or more logistics is sent to dethanizer 22；Deethanization
The C2 component that column overhead is isolated is sent to ethylene rectifying column 23 and further separates, and ethylene distillation column overhead isolates ethylene product
32, tower reactor isolates ethane product；Deethanizer bottoms stream is sent to depropanizing tower 24 and is separated, the separation of depropanizing tower tower top
C3 component out is sent to propylene rectification tower 25, and propylene rectification tower tower top isolates propylene product, the propane conduct that tower bottom is isolated
Recycle stock returns to propane gasification tank；Depropanizing tower tower bottom C4 and C4 or more component is sent to debutanizing tower 26 and is separated, and takes off fourth
Alkane column overhead isolates C4 component, and tower reactor isolates drippolene 35.
The integrated technique coupled using sequence separation ethylene unit with PDH, then ethylene total output is 81.29 ten thousand
Ton/year, propylene total output is 93.50 ten thousand tons/year, and product propylene/ethylene is than 1.15.Feed naphtha 278.64 ten thousand is consumed respectively
Ton/year, 62.93 ten thousand tons/year of fresh propane raw material.The integral method saves engineering construction investment 3.18 compared with comparative example 1
Hundred million yuans, reduce by 1.8 hectares of occupied area, but the opposite raising of ethylene unit machine utilization, see following table:
[comparative example 2]
The prior art separates ethylene unit by the sequence of cracking stock of naphtha, and nominal capacity is 1,000,000 tons/year.It should
Device ethylene yield is 100.00 ten thousand tons/year, and propylene yield is 52.00 ten thousand tons/year, and product propylene/ethylene ratio is 0.52.Consumption
348.30 ten thousand tons/year of raw material naphtha.
For the prior art using fresh propane as the PDH device of raw material, nominal capacity is 600,000 tons/year.Ethylene yield 1.29
Ten thousand tons/year, 51.90 ten thousand tons/year of propylene yield, fresh propane consumes 62.93 ten thousand tons/year.
[embodiment 2]
The integrated technique coupled using sequence separation ethylene unit with PDH, then ethylene total output is 101.29 ten thousand
Ton/year, propylene total output is 103.90 ten thousand tons/year, and product propylene/ethylene is than 1.03.Feed naphtha 348.30 is consumed respectively
Ten thousand tons/year, 62.93 ten thousand tons/year of fresh propane raw material.The integral method saves engineering construction investment compared with comparative example 2
3.96 hundred million yuans, reduce by 1.8 hectares of occupied area, but the opposite raising of ethylene unit machine utilization, see following table:
[comparative example 3]
The prior art separates ethylene unit by the sequence of cracking stock of naphtha, and nominal capacity is 1,100,000 tons/year.It should
Device ethylene yield is 110.00 ten thousand tons/year, and propylene yield is 57.20 ten thousand tons/year, and product propylene/ethylene ratio is 0.52.Consumption
383.13 ten thousand tons/year of raw material naphtha.
For the prior art using fresh propane as the PDH device of raw material, nominal capacity is 600,000 tons/year.Ethylene yield 1.29
Ten thousand tons/year, 51.90 ten thousand tons/year of propylene yield, fresh propane consumes 62.93 ten thousand tons/year.
[embodiment 3]
The integrated technique coupled using sequence separation ethylene unit with PDH, then ethylene total output is 111.29 ten thousand
Ton/year, propylene total output is 109.10 ten thousand tons/year, and product propylene/ethylene is than 0.98.Feed naphtha 383.13 is consumed respectively
Ten thousand tons/year, 62.93 ten thousand tons/year of fresh propane raw material.The integral method saves engineering construction investment compared with comparative example 1
4.05 hundred million yuans, reduce by 1.8 hectares of occupied area, but the opposite raising of ethylene unit machine utilization, see following table:
[comparative example 4]
The prior art separates ethylene unit by the sequence of cracking stock of naphtha, and nominal capacity is 1,200,000 tons/year.It should
Device ethylene yield is 120.00 ten thousand tons/year, and propylene yield is 62.40 ten thousand tons/year, and product propylene/ethylene ratio is 0.52.Consumption
417.97 ten thousand tons/year of raw material naphtha.
For the prior art using fresh propane as the PDH device of raw material, nominal capacity is 600,000 tons/year.Ethylene yield 1.29
Ten thousand tons/year, 51.90 ten thousand tons/year of propylene yield, fresh propane consumes 62.93 ten thousand tons/year.
[embodiment 4]
The integrated technique coupled using sequence separation ethylene unit with PDH, then ethylene total output is 121.29 ten thousand
Ton/year, propylene total output is 114.30 ten thousand tons/year, and product propylene/ethylene is than 0.94.Feed naphtha 417.97 is consumed respectively
Ten thousand tons/year, 62.93 ten thousand tons/year of fresh propane raw material.The integral method saves engineering construction investment compared with comparative example 1
4.89 hundred million yuans, reduce by 1.8 hectares of occupied area, but the opposite raising of ethylene unit machine utilization, see following table:
Above-mentioned [embodiment 1]~[embodiment 4] summarizes, and is shown in Table 1:
1 summary sheet of the embodiment of the present invention of table
Claims (8)
1. a kind of naphtha pyrolysis sequentially separates the method coupled with PDH technique, from the external fresh propane charging in battery limit (BL) and come
After recycled propane from de-oiling column overhead and the recycled propane mixing from propylene rectification tower tower bottom, enters propane jointly and gasify
Tank, tank bottom heavy constituent remove de-oiling Tower System and be ultimately sent to reaction gas industrial furnace make liquid supplement fuel, tank deck light component be sent into
PDH reactor, propane carry out dehydrogenation reaction in the reactor and generate the product gas for being rich in propylene, and the product gas after reaction is sent into second
The compression of alkene device and caustic wash unit；Cracking stock naphtha enters pyrolysis furnace, and cracking reaction occurs in pyrolysis furnace and generates packet
Pintsch process gas containing ethylene, cracking gas, which converges after chilling with the reactor product gas from PDH device, is sent into ethylene unit pressure
Contracting and caustic wash unit, are then successively separated through domethanizing column, dethanizer, depropanizing tower, debutanizing tower, C2 group is distributed into
Ethylene rectifying column carries out isolated ethylene product, and C3 group is distributed into propylene rectification tower and carries out isolated propylene product.
2. naphtha pyrolysis sequentially separates the method coupled with PDH technique according to claim 1, it is characterised in that ethylene dress
Setting nominal capacity is 80~1,200,000 tons/year, and product propylene/ethylene ratio is 0.52.
3. naphtha pyrolysis sequentially separates the method coupled with PDH technique according to claim 1, it is characterised in that PDH dress
Setting nominal capacity is 600,000 tons/year, produces 1.29 ten thousand tons/year of ethylene product, produces 51.90 ten thousand tons/year of propylene product.
4. naphtha pyrolysis sequentially separates the method coupled with PDH technique according to claim 1, it is characterised in that ethylene dress
Set the operating condition of pyrolysis furnace are as follows: 0.10~0.25MPaA of reaction pressure, 810~870 DEG C of reaction temperature.
5. naphtha pyrolysis sequentially separates the method coupled with PDH technique according to claim 1, it is characterised in that PDH dress
Set the operating condition of reactor are as follows: 0.10~0.35MPaA of reaction pressure, 500~700 DEG C of reaction temperature.
6. naphtha pyrolysis sequentially separates the method coupled with PDH technique according to claim 1, it is characterised in that propane flammable gas
Change after tank tank deck light component is heated to reaction temperature into heating furnace after preheating as reaction feed and is sent into PDH reactor.
7. naphtha pyrolysis sequentially separates the method coupled with PDH technique according to claim 6, it is characterised in that propane flammable gas
Change after tank tank deck light component is heated to reaction temperature into heating furnace after being preheated to 180~260 DEG C as reaction feed and send
Enter PDH reactor.
8. naphtha pyrolysis sequentially separates the method coupled with PDH technique according to claim 1, it is characterised in that sufficiently according to
Support ethylene unit existing equipment is separated, and ethylene unit equipment component produce load is opposite to be improved, but PDH device uses
Equipment reduce, eliminate product air compressor, product gas dry gas, dethanizer feed drier, dethanizer, ice chest system
System, propylene rectification tower, propylene rectification tower feed desulfurization bed, ethylene refrigeration compressor, propylene refrigeration compressor.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114057534A (en) * | 2020-08-07 | 2022-02-18 | 中国石油天然气集团有限公司 | Catalytic cracking product separation device and separation method |
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| CN107602323A (en) * | 2017-10-11 | 2018-01-19 | 中石化上海工程有限公司 | The method that dehydrogenating propane technique couples with light hydrocarbon cracking predepropanization technique |
| CN107673947A (en) * | 2017-10-11 | 2018-02-09 | 中石化上海工程有限公司 | The method that dehydrogenating propane technique couples with naphtha pyrolysis front-end deethanization technique |
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Application publication date: 20190607 |