CN109534946A - Naphtha and ethane cracking sequentially separate the method coupled with MTO - Google Patents
Naphtha and ethane cracking sequentially separate the method coupled with MTO Download PDFInfo
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- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
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- C07C4/00—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms
- C07C4/02—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by cracking a single hydrocarbon or a mixture of individually defined hydrocarbons or a normally gaseous hydrocarbon fraction
- C07C4/04—Thermal processes
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Abstract
The present invention relates to a kind of naphthas and ethane cracking sequentially to separate the method coupled with MTO, mainly solves the problems, such as that naphtha in the prior art and ethane feed consumption are big, propylene yield is few, by-product quantity is more, production run is at high cost.The present invention sequentially separates the method coupled with MTO by using a kind of naphtha and ethane cracking, rely on ethylene unit sequence separating technology process, 100~1,200,000 tons/year of ethylene units are coupled with 1,800,000 tons/year of MTO devices, lapidation cerebrol and ethane 78.55~117.92 ten thousand ton/year, propylene enhancing 13.23~24.52 ten thousand ton/year can be lacked；Increase economic benefit 2.9~12.9 hundred million yuans/year technical solutions and preferably solve the above problem, can be used for naphtha and ethane cracking sequence separation is coupled with MTO.
Description
Technical field
The present invention relates to a kind of naphthas and ethane cracking sequentially to separate the method coupled with MTO.Rely on existing sequence point
Separating process process ethylene producing device substitutes part naphtha and ethane by raw material of methanol, can effectively improve propylene production capacity,
Yield of light olefins is improved, by-product quantity is reduced and reduces production run cost, can be applied to the industrial production of low-carbon alkene
In.
Background technique
Ethylene is mainly obtained by cracking naphtha and lighter hydrocarbons, ordinary pressure diesel, hydrogenation tail oil etc., is petrochemical industry row
The foundation stone of industry, therefore the development of cracking technology technology is most important for ethylene unit.By long-term research with exploitation, crack
Furnace technology reaches its maturity, towards expand the scale of production, improve cracking severity, shorten the residence time, increase cracking stock variation and
Operating flexibility etc. development extends operation operation cycle, reduces the comprehensive energy of device to improve pyrolysis furnace to the adaptability of raw material
Consumption.102051206 A of CN in the prior art is related to a kind of method of producing ethylene cracking materials by hydrofining naphtha, mentions
The high quality of the naphtha of secondary operation.105349172 A of CN is related to a kind of catalytic cracking method of feed naphtha, drop
Low non-ideal product yield.105585399 A of 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.
Separation process is one of core process of ethylene production, is broadly divided into three categories technology, i.e. sequence isolation technics, preceding
Deethanization technology and predepropanization technology.Three types of technology respectively has speciality, wherein the separation process of existing ethylene producing device uses
Sequence isolation technics includes: the hydro carbons in cracking gas containing different molecular weight, and each component is successively separated according to sequence from light to heavy,
It is introduced into domethanizing column, tower top isolates methane and hydrogen, and tower reactor isolates carbon two and two or more group of carbon is distributed into dethanizer,
Deethanization tower top isolates two groups of dispensing ethylene rectifying columns of carbon, and ethylene distillation tower top isolates polymer grade ethylene product, deethanization
Tower bottoms is sent to depropanizing tower, and depropanization tower top isolates three groups of dispensing propylene rectification towers of carbon, and propylene rectification tower top is isolated poly-
Grade propylene product is closed, depropanizing tower kettle liquid is sent to debutanizing tower, and debutanization tower top isolates four component of carbon, and tower bottoms is cracked
Gasoline.
Since petroleum resources are in short supply, price fluctuation is huge, using UOP/Hydro methanol-to-olefins MTO technique as the non-of representative
Petroleum path ethylene process technology has gradually developed.MTO technique includes the MTO technique of Mobil Corporation and Uop Inc. in the world
And the MTP technique of Lucci corporation.The domestic Chinese Academy of Sciences Dalian Chemistry and Physics Institute, Shaanxi emerging coal chemical industry development in science and technology Co., Ltd, in
Petrochemical industry Luoyang engineering company joint development has prepared light olefin technology DMTO at home by the catalysis reaction of one step of raw material of methanol
Success carries out industrialization large-scale production application.
Gradually increase about the research of MTO technique and application in recent years.101921161 A of CN relates to methanol-to-olefins
MTO gas separating technology process has many advantages, such as that investment is low, operating cost is low, ethylene loss is few.204138566 U of CN is disclosed
A kind of purification system of MTO grades of methanol.107602328 A of CN is related to a kind of four pre-separation technique of MTO device by-product carbon.
101381270A provides a kind of separation method of MTO/MTP reaction mixture.Patent of invention CN 104193574 B, CN
104151121 B、CN 107056575 A、CN 107417481 A、CN 107056568 A、CN 104193570 B、CN
104230617 B have all referred to the coupling technique of MTO device and ethylene unit.
Patent of invention CN in the prior art 104193574 B, CN 104151121 B, CN 107056575 A, CN
107417481 A and 107056568 A of CN relate to the coupling of MTO device and ethylene unit, but there is no be directed to ethylene unit
Sequence separating technology process；104230617 B of patent of invention CN 104193570 B and CN relates to MTO technique and ethylene fills
The method for setting the coupling of sequence separating technology, but there is no select the cracking stock of naphtha and ethane as ethylene unit.Therefore,
Prior art naphtha pyrolysis sequence separating technology ethylene unit coupled with MTO device there are naphtha and ethane feed consumption
Greatly, the problem that propylene yield is few, by-product quantity is more, production run is at high cost.
Summary of the invention
Big, propylene yield that the technical problem to be solved by the present invention is to naphthas in the prior art and ethane feed consumption
Less, the problem that by-product quantity is more, production run is at high cost, provide a kind of new naphtha and the separation of ethane cracking sequence with
The method of MTO coupling, there is naphtha and ethane feed to consume, and small, propylene yield is more, by-product quantity is few, production run cost
Low advantage.
To solve the above problems, The technical solution adopted by the invention is as follows: a kind of naphtha and ethane cracking sequence separate
The method coupled with MTO, ethylene unit: cracking stock naphtha and ethane enter pyrolysis furnace and the generation of steam heat scission reaction occur
Cracking gas including ethylene, propylene send compressional zone to be pressurized after cracking gas enters chilling area progress quenching；Chilling area
Isolate heavy constituent drippolene and Pyrolysis fuel oil PFO；After pressurized cracking gas material merges with the material from MTO device
It is sent into domethanizing column, tower top isolates methane and hydrogen, and the C2 and C2 or more group that tower reactor is isolated are distributed into dethanizer；De- second
The C2 material that alkane tower top is isolated is sent into ethylene rectifying column, and tower top isolates polymer grade ethylene product, and tower reactor isolates ethane object
Material；Dethanizer tower reactor isolates C3 and C3 or more heavy constituent material and is sent into depropanizing tower；The C3 object that depropanization tower top is isolated
Material is sent into propylene rectification tower, and tower top isolates polymerization-grade propylene product, and tower reactor isolates propane materials；The separation of depropanizing tower tower reactor
C4 and C4 or more heavy constituent material is sent into debutanizing tower out；Debutanization tower top isolates C4 component, tower reactor isolate C5 and C5 with
Upper heavy constituent drippolene；MTO device: methanol feedstock send MTO reaction member that catalysis reaction occurs to generate to include ethylene, propylene
Product gas；Product gas material is sent into MTO pre-separation unit and is separated, and part C3 and C3 or less light component material send ethylene unit
Domethanizing column is further processed；Remaining C3 and C3 or more heavy constituent material enters MTO device depropanizing tower and is separated, depropanization
Overhead stream enters the propylene rectification tower in MTO device, and propylene rectification tower top obtains polymerization-grade propylene product, and tower reactor obtains third
Alkane；Depropanization tower reactor logistics is sent to ethylene unit, and ethylene unit debutanizing tower is relied on further to separate.
In above-mentioned technical proposal, it is preferable that ethylene unit: nominal capacity 100~1,200,000 ton/year, naphtha account for raw material matter
The 70% of amount；Ethane accounts for the 30% of material quality.
In above-mentioned technical proposal, it is preferable that MTO device: 1,800,000 tons/year of nominal capacity, response intensity: ethylene/propene matter
Measure ratio=0.8~1.5.
In above-mentioned technical proposal, it is preferable that naphtha and ethane cracking ethylene unit use sequence separating technology, ethane
Steam cracking furnace is respectively enterd as cracking stock with naphtha and carries out cracking reaction, cracks selective propylene/ethylene mass ratio
=0.34.
In above-mentioned technical proposal, it is preferable that the operating condition of the pre-separation unit are as follows: operating pressure 0.6~
3.0MPaA, operation temperature -30~15 DEG C.
In above-mentioned technical proposal, it is preferable that the product gas that MTO reaction member generates is divided into two after pre-separation unit
Stock, the ratio between first strand and the mass flow of second burst of product gas are 1.2~2.6:1.
In the present invention, the operating condition of MTO reaction member are as follows: 0.15~0.50MPaA of reaction pressure, reaction temperature 400~
550℃；The operating condition of Furnace of Ethylene Cracking Plant are as follows: 0.10~0.25MPaA of reaction pressure, 810~870 DEG C of reaction temperature.
The technical problems to be solved by the invention be exactly prior art naphtha pyrolysis sequence separating technology ethylene unit with
That there are naphthas and ethane feed consumption is big for the coupling of MTO device, propylene yield is few, by-product quantity is more, production run is at high cost
The problem of.A kind of method that new MTO technique is coupled with naphtha and ethane cracking sequence separating technology is provided, this method uses
Methanol substitutes part naphtha and ethane, reduces naphtha and ethane feed consumption, increases propylene yield, reduces by-product
Object quantity, to reducing production run cost.The present invention relies on ethylene unit sequence separating technology process, with methanol substitution portion
Divide the integrated coupling process method propylene enhancing product of naphtha and ethane.For 100~1,200,000 tons/year of ethylene units and
For 1800000 tons/year of MTO devices, lapidation cerebrol 54.99~82.54 ten thousand ton/year can be lacked, throw ethane 23.57~35.38 ten thousand less
Ton/year, propylene enhancing 13.23~24.52 ten thousand ton/year；Simultaneously product and raw material price difference save 2.9~12.9 hundred million yuans/
Year, achieve preferable economic benefit.
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]
Existing naphtha and the ethylene unit of ethane steam thermal cracking sequence separation.Wherein, naphtha accounts for the matter of material quantity
Score 70% is measured, ethane accounts for the mass fraction 30% of material quantity；Ethylene production capacity is 1,200,000 tons/year, polymer grade ethylene purity >=
99.95mol%；Propylene production capacity is 40.80 ten thousand tons/year, polymerization-grade propylene purity >=99.6mol%.Consume naphtha and ethane
349.91 ten thousand tons/year of raw material, wherein naphtha consumes 244.93 ten thousand tons/year, and ethane consumes 104.97 ten thousand tons/year.
[embodiment 1]
The method coupled with MTO is sequentially separated using a kind of naphtha of the present invention and ethane cracking, process flow is as follows: second
Alkene device: cracking stock naphtha and ethane enter pyrolysis furnace and the materials such as steam heat scission reaction generation ethylene, propylene occur, and split
After the Pintsch process gas of solution outlet of still enters chilling area progress quenching, compressional zone is sent to be pressurized；Chilling differentiation separates out
Heavy constituent drippolene and Pyrolysis fuel oil PFO；Pressurized cracking gas material is sent into de- after merging with the material from MTO device
Methane tower, tower top isolate methane and hydrogen, and the C2 and C2 or more group that tower reactor is isolated are distributed into dethanizer；Deethanization tower top
C2 material is isolated, which send ethylene rectifying column, and tower top isolates polymer grade ethylene product, and tower reactor isolates ethane material；
Dethanizer tower reactor isolates C3 and C3 or more heavy constituent material and is sent into depropanizing tower；Depropanization tower top isolates C3 material, should
Material send propylene rectification tower, and tower top isolates polymerization-grade propylene product, and tower reactor isolates propane materials；The separation of depropanizing tower tower reactor
C4 and C4 or more heavy constituent material is sent into debutanizing tower out；Debutanization tower top isolates C4 component, tower reactor isolate C5 and C5 with
Upper heavy constituent drippolene.MTO device: methanol feedstock send MTO reaction member that catalysis reaction occurs and generates the low-carbons such as ethylene, propylene
Alkene；Product gas material is sent into MTO separative unit and is separated, and part C3 and C3 or less light component material send ethylene unit piptonychia
Alkane tower is further processed；Remaining C3 and C3 or more heavy constituent material enters MTO device depropanizing tower and is separated, depropanization tower top
Logistics enters the propylene rectification tower in MTO device, and propylene rectification tower top obtains polymerization-grade propylene product, and tower reactor obtains propane；It is de-
Propane tower reactor logistics is sent to ethylene unit, and ethylene unit debutanizing tower is relied on further to be separated.
Using 70% naphtha of mass fraction and 30% ethane steam of mass fraction as raw material, using sequence separating technology second
Alkene, the nominal capacity of device are 1,200,000 tons/year.Methanol-to-olefins MTO device production scale is 1,800,000 tons/year, product ethylene/
Propylene mass ratio is 1.5.The operating condition of coupling device crude separation tower are as follows: -15 DEG C of temperature, pressure 1.2MPaG.Coupling device second
Alkene production capacity is 1,200,000 tons/year, polymer grade ethylene purity >=99.95mol%；Coupling device propylene production capacity is 54.00 ten thousand tons/year,
Polymerization-grade propylene purity >=99.6mol%.Compared to comparative example 1,13.20 ten thousand tons/year of propylene enhancing, lack lapidation cerebrol 82.54
Ten thousand tons/year, 35.38 ten thousand tons/year of ethane are thrown less.Product and raw material price difference can save 12.9 hundred million yuans/year.
[comparative example 2]
The nominal capacity of ethylene unit is 1,100,000 tons/year, remaining condition and step are identical with [comparative example 1].Propylene
Production capacity is 37.40 ten thousand tons/year.Naphtha and 320.75 ten thousand tons/year of ethane feed are consumed, wherein naphtha consumption 224.52 ten thousand
Ton/year, ethane consumes 96.22 ten thousand tons/year.
[embodiment 2]
The nominal capacity of ethylene unit is only changed to 1,100,000 tons/year, remaining condition and step and [embodiment 1] are completely
It is identical.Coupling device propylene production capacity is 50.61 ten thousand tons/year, 13.21 ten thousand tons/year of propylene enhancing, few to throw compared to [comparative example 2]
82.54 ten thousand tons/year of naphtha, 35.38 ten thousand tons/year of ethane are thrown less.Product and raw material price difference can save 12.9 hundred million yuans/
Year.
[comparative example 3]
The nominal capacity of ethylene unit is 1,000,000 tons/year, remaining condition and step are identical with [comparative example 1].Propylene
Production capacity is 34.00 ten thousand tons/year.Naphtha and 291.59 ten thousand tons/year of ethane feed are consumed, wherein naphtha consumption 204.11 ten thousand
Ton/year, ethane consumes 87.48 ten thousand tons/year.
[embodiment 3]
The nominal capacity of ethylene unit is only changed to 1,000,000 tons/year, remaining condition and step and [embodiment 1] are completely
It is identical.Coupling device propylene production capacity is 47.21 ten thousand tons/year, 13.21 ten thousand tons/year of propylene enhancing, few to throw compared to [comparative example 3]
82.54 ten thousand tons/year of naphtha, 35.38 ten thousand tons/year of ethane are thrown less.Product and raw material price difference can save 12.9 hundred million yuans/
Year.
[embodiment 4]
According to the condition and step of [embodiment 3], only product gas ethylene/propene mass ratio in MTO device is changed by 1.5
It is 1.2.Coupling device propylene production capacity is 51.48 ten thousand tons/year, 17.48 ten thousand tons/year of propylene enhancing, few compared to [comparative example 3]
72.34 ten thousand tons/year of lapidation cerebrol, 31.00 ten thousand tons/year of ethane are thrown less.Product and raw material price difference can save 9.3 hundred million yuans/
Year.
[embodiment 5]
According to the condition and step of [embodiment 3], only product gas ethylene/propene mass ratio in MTO device is changed by 1.5
It is 1.0.Coupling device propylene production capacity is 54.70 ten thousand tons/year, 20.70 ten thousand tons/year of propylene enhancing, few compared to [comparative example 3]
64.07 ten thousand tons/year of lapidation cerebrol, 27.46 ten thousand tons/year of ethane are thrown less.Product and raw material price difference can save 6.2 hundred million yuans/
Year.
[embodiment 6]
According to the condition and step of [embodiment 3], only product gas ethylene/propene mass ratio in MTO device is changed by 1.5
It is 0.9.Coupling device propylene production capacity is 56.50 ten thousand tons/year, 22.50 ten thousand tons/year of propylene enhancing, few compared to [comparative example 3]
59.60 ten thousand tons/year of lapidation cerebrol, 25.54 ten thousand tons/year of ethane are thrown less.Product and raw material price difference can save 4.5 hundred million yuans/
Year.
[embodiment 7]
According to the condition and step of [embodiment 3], only product gas ethylene/propene mass ratio in MTO device is changed by 1.5
It is 0.8.Coupling device propylene production capacity is 58.49 ten thousand tons/year, 24.49 ten thousand tons/year of propylene enhancing, few compared to [comparative example 3]
54.99 ten thousand tons/year of lapidation cerebrol, 23.57 ten thousand tons/year of ethane are thrown less.Product and raw material price difference can save 2.9 hundred million yuans/
Year.
Above-described embodiment summarizes, and is shown in Table 1.
1 embodiment summary sheet of table
Claims (7)
1. a kind of naphtha and ethane cracking sequentially separate the method coupled with MTO, ethylene unit: cracking stock naphtha and second
Alkane enters pyrolysis furnace and the cracking gas that the generation of steam heat scission reaction includes ethylene, propylene occurs, and cracking gas enters the progress of chilling area
After quenching, compressional zone is sent to be pressurized；Chilling differentiation separates out heavy constituent drippolene and Pyrolysis fuel oil PFO；It is pressurized to split
It vents one's spleen after material merges with the material from MTO device and is sent into domethanizing column, tower top isolates methane and hydrogen, and tower reactor is isolated
C2 and C2 or more group be distributed into dethanizer；The C2 material that deethanization tower top is isolated is sent into ethylene rectifying column, tower top separation
Polymer grade ethylene product out, tower reactor isolate ethane material；Dethanizer tower reactor is isolated C3 and C3 or more heavy constituent material and is sent
Enter depropanizing tower；The C3 material that depropanization tower top is isolated is sent into propylene rectification tower, and tower top isolates polymerization-grade propylene product, tower
Kettle isolates propane materials；Depropanizing tower tower reactor isolates C4 and C4 or more heavy constituent material and is sent into debutanizing tower；Debutanizing tower
C4 component is isolated on top, and tower reactor isolates C5 and C5 or more heavy constituent drippolene；MTO device: methanol feedstock send MTO reaction single
The product gas that catalysis reaction generation includes ethylene, propylene occurs for member；Product gas material is sent into MTO pre-separation unit and is separated,
Part C3 and C3 or less light component material send ethylene unit domethanizing column to be further processed；Remaining C3 and C3 or more heavy constituent material
It is separated into MTO device depropanizing tower, depropanization overhead stream enters the propylene rectification tower in MTO device, propylene rectifying
Tower top obtains polymerization-grade propylene product, and tower reactor obtains propane；Depropanization tower reactor logistics is sent to ethylene unit, relies on ethylene unit de-
Butane tower further separates.
2. naphtha and ethane cracking sequentially separate the method coupled with MTO according to claim 1, it is characterised in that ethylene
Device: nominal capacity 100~1,200,000 ton/year, naphtha account for the 70% of material quality；Ethane accounts for the 30% of material quality.
3. naphtha and ethane cracking sequentially separate the method coupled with MTO according to claim 1, it is characterised in that MTO
Device: 1,800,000 tons/year of nominal capacity.
4. naphtha and ethane cracking sequentially separate the method coupled with MTO according to claim 1, it is characterised in that stone brain
Oil and ethane cracking ethylene unit respectively enter steam as cracking stock using sequence separating technology, ethane and naphtha and split
It solves furnace and carries out cracking reaction, crack selective propylene/ethylene mass ratio=0.34.
5. naphtha and ethane cracking sequentially separate the method coupled with MTO according to claim 1, it is characterised in that MTO
Device: response intensity: ethylene/propene mass ratio=0.8~1.5.
6. naphtha and ethane cracking sequentially separate the method coupled with MTO according to claim 1, it is characterised in that described
The operating condition of pre-separation unit are as follows: 0.6~3.0MPaA of operating pressure, operation temperature -30~15 DEG C.
7. naphtha and ethane cracking sequentially separate the method coupled with MTO according to claim 1, it is characterised in that MTO
The product gas that reaction member generates is divided into two strands after pre-separation unit, first strand with the mass flow of second burst of product gas it
Than for 1.2~2.6:1.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104193570A (en) * | 2014-08-13 | 2014-12-10 | 中石化上海工程有限公司 | MTO process and naphtha cracking sequence separating process coupling method |
| CN104230617A (en) * | 2014-08-13 | 2014-12-24 | 中石化上海工程有限公司 | Method for coupling MTO process and naphtha and propane cracking progressive separation process |
-
2018
- 2018-12-10 CN CN201811502974.4A patent/CN109534946A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104193570A (en) * | 2014-08-13 | 2014-12-10 | 中石化上海工程有限公司 | MTO process and naphtha cracking sequence separating process coupling method |
| CN104230617A (en) * | 2014-08-13 | 2014-12-24 | 中石化上海工程有限公司 | Method for coupling MTO process and naphtha and propane cracking progressive separation process |
Non-Patent Citations (2)
| Title |
|---|
| 徐蔚: "甲醇制烯烃与前脱丙烷乙烯工艺一体化的研究", 《化工与医药工程》 * |
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