CN109809957A - The method that light hydrocarbon cracking front-end deethanization technique is coupled with PDH technique - Google Patents
The method that light hydrocarbon cracking front-end deethanization technique is coupled with PDH technique Download PDFInfo
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- 239000001273 butane Substances 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
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- 230000000052 comparative effect Effects 0.000 description 14
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- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
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- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
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Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/40—Ethylene production
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The present invention relates to a kind of method that light hydrocarbon cracking front-end deethanization technique is coupled with PDH technique, engineering construction investment height in the prior art is mainly solved, is taken up a large area, the low problem of propene yield.The present invention is by using a kind of method that light hydrocarbon cracking front-end deethanization technique is coupled with PDH technique, 80~1,200,000 tons/year of ethylene units are coupled with 600,000 tons/year of PDH devices to optimize product structure, propylene/ethylene ratio increases to 0.67~0.88 by 0.23, reduce equipment investment 4.64~9.16 hundred million yuan, it reduces by 1.8 hectares of occupied area of technical solution and preferably solves the above problem, can be used for during light hydrocarbon cracking front-end deethanization technique couples with PDH technique.
Description
Technical field
The present invention relates to a kind of methods that light hydrocarbon cracking front-end deethanization technique is coupled with PDH technique, are dehydrogenating propane PDH dresses
The method of the technology set coupling integrated with the technology of light hydrocarbon cracking ethylene unit of front-end deethanization separating technology.It should
PDH device only retains dehydrogenation reaction part and product gas preprocessing part in method, other separation equipments rely on ethylene unit
Separation equipment, not only reduce equipment investment and occupied area, but also effective propylene enhancing, solve light hydrocarbon cracking ethylene unit and produce
The single problem of product structure, can be applied to prepare in the industrial production of ethylene.
Background technique
Ethylene is the basic organic chemical industry raw material for preparing synthetic plastic, synthetic rubber, synthetic fibers, is also used for manufacture chloroethene
Products such as alkene, styrene, ethylene oxide, ethyl alcohol, acetaldehyde, acetic acid, and be a kind of certified plant hormone, can be used as fruit and
The ripener of vegetables.Currently, ethylene is also one of maximum chemical products of yield in the world, ethylene industry is petrochemical industry
Core, ethylene product accounts for the half of the country of petrochemicals, occupies an important position in national economy, incited somebody to action in the world
Ethylene yield is as the important symbol for measuring a national oil development of chemical industry level.
Propylene can be used for producing a variety of importantization as ethylene and one of petrochemical industry basic organic chemical industry raw material
Product is learned, such as: acrylonitrile, propylene oxide, isopropylbenzene, epoxychloropropane, isopropanol, propylene glycol, acetone, butanol, octanol, propylene
Aldehyde, acrylic acid, propenyl, glycerol etc.；It is the raw material for producing polymer gasoline in petroleum refining industry；Can also generate synthetic plastic,
Synthetic rubber, synthetic fibers and a variety of fine chemistry products of production, for the neck such as environmental protection, medical science and basic research
Domain.
Ethylene unit is using petroleum or lighter hydrocarbons as raw material, and to produce based on high-purity ethylene and propylene, while by-product is a variety of
The petrochemical plant of petrochemical materials.Cracking stock passes through Pintsch process, compression, isolated ethylene in ethylene unit
Product, while obtaining the byproducts such as propylene, butadiene, benzene, toluene and dimethylbenzene.Ethylene unit is former as cracking using lighter hydrocarbons
Material, is important one of the developing direction of ethylene unit.Yield of ethene is higher after raw material lighting, and cracking cost is lower, cracking gas
Ingredient is also simpler, is easy to rectifying separation, is the effective means for improving ethylene unit operation income.
Dehydrogenating propane PDH device is that propane catalytic dehydrogenating reaction is generated to main group to become propylene and unreacted propane
Product gas, product gas are sent outside by the isolated propylene of deep cooling process for separating and propane, propylene as product, and propane cycles return
As dehydrogenation feed.The rectifying separation process and the separation process of ethylene unit of PDH device are very similar, therefore, completely can be according to
Hold in the palm the rectifying separation equipment of ethylene unit.
201710939515.1 dehydrogenating propane technique of patent of invention in the prior art and light hydrocarbon cracking predepropanization technique
The method of coupling, the method that 201710939541.4 dehydrogenating propane techniques are coupled with naphtha pyrolysis front-end deethanization technique,
The method that 201710939558.X dehydrogenating propane technique is coupled with naphtha pyrolysis predepropanization technique, is related to dehydrogenating propane device
The coupling of separating technology and ethylene unit separating technology discloses and leverages fully on the progress material rectifying point of ethylene unit separation equipment
From technical method.
Lighter hydrocarbons in the prior art are single as cracking stock ethylene unit product structure, and propylene/ethylene mass ratio is low；
PDH device separation process is tediously long, and separation equipment investment is high, and process units takes up a large area.And patent of invention in the prior art
201710939515.1 and 201710939541.4 and 201710939558.X has no dehydrogenating propane device technique and preceding de- second
The technical method of alkane disjunctive path light hydrocarbon cracking ethylene unit technique coupling.Therefore, there are propylene low outputs, engineering for the prior art
The problem that investment is high, occupation area of equipment is big.
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 a kind of method that new light hydrocarbon cracking front-end deethanization technique is coupled with PDH technique, there is engineering construction to throw
Provide 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 light hydrocarbon cracking front-end deethanization technique and PDH
The method of technique coupling, comprising: (1) ethylene unit: cracking reaction occurs for light hydrocarbon cracking raw material generate in pyrolysis furnace to include second
The cracking gas of alkene, propylene, cracking gas merge after over-quenching, compression, alkali cleaning, drying, deep cooling with PDH device product gas, enter
Rectifying separation system；(2) PDH device: raw material propane and the recycled propane from de-oiling column overhead and propylene rectification tower bottom are third
Gasification in alkane gasification tank, the discharging of gasification tank gas phase is heated to dehydrogenation reaction temperature in heating furnace, into dehydrogenation reactor, dehydrogenation
Product gas is sent after compression, drying, deep cooling to ethylene unit rectifying separation system, and gasification tank bottom liquid phases enter de-oiling tower and return
It receives, overhead condensation liquid returns to propane gasification tank, and C4 and C4 or more the group of tower reactor are sent to ethylene unit debutanizing tower；(3) it couples
Device: ethylene cracking gas and PDH device product gas enter dethanizer, and tower top isolates C2 and C2 following components, enter
Domethanizing column, tower bottom isolate C3 and C3 or more component, into depropanizing tower；Demethanation tower top isolates methane hydrogen byproduct
It sends out out-of-bounds, tower bottom isolates C2 component, into ethylene rectifying column；Ethylene distillation tower top is isolated ethylene product and is sent out out-of-bounds,
Tower bottom isolates ethane, is recycled back into ethylene unit cracking unit；Depropanization tower top isolates C3 component, into propylene rectifying
Tower, tower bottom isolate C4 and C4 or more component, mix with PDH device de-oiling tower tower base stream, into debutanizing tower；Propylene rectifying
Tower top isolates propylene, sends out out-of-bounds as product, tower bottom isolates propane, is recycled back into PDH device propane gasification tank；De- third
Alkane materials at bottom of tower and de-oiling materials at bottom of tower are mixed into debutanizing tower, and C4 component is isolated in tower top rectifying, send out boundary as product
Outside, tower bottom isolates C5 and C5 or more component, and submitting is merged with the drippolene that quenching unit is isolated out-of-bounds.
In above-mentioned technical proposal, it is preferable that ethylene unit nominal capacity: 80~1,200,000 tons/year, cracking stock lighter hydrocarbons by
40% ethane, 30% propane, 30% butane composition, coupling device product propylene/ethylene mass ratio P/E=0.23.
In above-mentioned technical proposal, it is preferable that PDH device nominal capacity: 600,000 tons/year.
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 rectifying separation system using front-end deethanization route to cracking gas and product gas into
Row rectifying separation.
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 eliminates dethanizer, cold box system, propylene essence
Evaporate tower, propylene rectification tower charging desulfurization bed, ethylene refrigeration compressor, propylene refrigeration compressor.
The main purpose of the present invention is to solve steamcracker feed ethylene unit unreasonable products structure, propylene low output,
The problem that PDH device separation process is tediously long, construction investment is high, occupation area of equipment is big.Before the present invention passes through a kind of light hydrocarbon cracking
The method that deethanization technique is coupled with PDH technique increases a set of PDH device reaction system newly, leverages fully on ethylene unit separation and sets
It is standby to carry out material rectifying separation, to effectively optimize the product structure of front-end deethanization route light hydrocarbon cracking ethylene unit.The party
Method increases propylene yield, reduces equipment investment, reduces occupied area.Using technical method of the invention, front-end deethanization
The light hydrocarbon cracking ethylene unit of route increases a set of PDH device reaction system newly, and ethylene yield is constant, critical product specification keeping
Under conditions of constant, relative to independently construction ethylene unit and PDH device, 80~1,200,000 tons/year of ethylene units and 600,000
The coupling of ton/year PDH device, can optimize product structure, and propylene/ethylene ratio increases to 0.67~0.88 by 0.23, reduce equipment
Gross investment 4.64~9.16 hundred million yuan reduce about 1.8 hectares of occupied area, achieve preferable technical effect and economic effect
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]
The ethylene unit that 1,200,000 tons/year of nominal capacity, using front-end deethanization separation process, cracking stock by 40% ethane,
30% propane, 30% butane composition, propylene/ethylene ratio=0.23,120.00 ten thousand tons/year of ethylene product yield, propylene product produces
Measure 27.60 ten thousand tons/year, 292.45 ten thousand tons/year of cracking stock consumption.
[embodiment 1]
Using a kind of method that light hydrocarbon cracking front-end deethanization technique is coupled with PDH technique of the present invention, process flow is as follows:
(1) ethylene unit: the light hydrocarbon cracking raw material being made of ethane, propane, butane occur in pyrolysis furnace cracking reaction generate ethylene,
The cracking gas of the materials such as propylene, butadiene, benzene, toluene and dimethylbenzene, Pintsch process gas through over-quenching, washing etc. pretreatment after,
Drippolene and Pyrolysis fuel oil PFO is isolated to send out out-of-bounds as byproduct.Cracking gas is through overcompression, alkali cleaning, drying, deep cooling etc.
Merge after pretreatment with PDH device product gas, into rectifying separation system.(2) PDH device: fresh propane raw material and carry out autospasy
Oily column overhead and the recycled propane at propylene rectification tower bottom gasify in propane gasification tank, and the discharging of gasification tank gas phase adds in heating furnace
Heat is to dehydrogenation reaction temperature, into dehydrogenation reactor.The composition predominantly dehydrogenation product gas of propylene and unreacted propane is through pressing
After the pretreatment such as contracting, drying, deep cooling, send to ethylene unit rectifying separation system.Gasification tank bottom liquid phases enter the recycling of de-oiling tower,
Overhead condensation liquid returns to propane gasification tank, and C4 and C4 or more the group of tower reactor are sent to ethylene unit debutanizing tower.(3) coupling dress
Set: ethylene cracking gas and PDH device product gas enter dethanizer, and tower top isolates C2 and C2 following components, into de-
Methane tower, tower bottom isolate C3 and C3 or more component, into depropanizing tower；Demethanation tower top is isolated methane hydrogen byproduct and is sent
Outside out-of-bounds, tower bottom isolates C2 component, into ethylene rectifying column；Ethylene distillation tower top is isolated ethylene product and is sent out out-of-bounds, tower
Ethane is isolated at bottom, is recycled back into ethylene unit cracking unit；Depropanization tower top isolates C3 component, into propylene rectification tower,
Tower bottom isolates C4 and C4 or more component, mixes with PDH device de-oiling tower tower base stream, into debutanizing tower；Propylene rectification tower
Propylene is isolated on top, is sent out out-of-bounds as product, tower bottom isolates propane, is recycled back into PDH device propane gasification tank；Depropanization
Materials at bottom of tower and de-oiling materials at bottom of tower are mixed into debutanizing tower, and C4 component is isolated in tower top rectifying, send out out-of-bounds as product,
Tower bottom isolates C5 and C5 or more component, and submitting is merged with the drippolene that quenching unit is isolated out-of-bounds.
60 tons/year of PDH device nominal capacity, 2.52 ten thousand tons/year of ethylene yield, 54.60 ten thousand tons/year of propylene yield.Ethylene
Device and PDH device coupling after ethylene total output be 122.52 ten thousand tons/year, 82.20 ten thousand tons/year of propylene yield, integrated apparatus
68.46 hundred million yuans of engineering construction investment.Compared with [comparative example 1], integration transformation after 54.60 ten thousand tons of propylene enhancing/
Year, ethylene yield increases by 2.10%, and propylene yield increases by 197.8%, and engineering is saved in propylene/ethylene product quality ratio=0.67
9.16 hundred million yuans of construction investment, it is equivalent to investment reduction 11.80%, reduces about 1.8 hectares of occupied area.Embodiment 1 is set
The variation of standby load and 1 machine utilization of comparative example, is shown in Table 1.
1 machine utilization of table promotes list
[comparative example 2]
The ethylene unit that 1,100,000 tons/year of nominal capacity, using front-end deethanization separation process, cracking stock by 40% ethane,
30% propane, 30% butane composition, propylene/ethylene ratio=0.23,110.00 ten thousand tons/year of ethylene product yield, propylene product produces
Measure 25.30 ten thousand tons/year, 268.08 ten thousand tons/year of cracking stock consumption.
[embodiment 2]
60 tons/year of PDH device nominal capacity, 2.52 ten thousand tons/year of ethylene yield, 54.60 ten thousand tons/year of propylene yield.Ethylene
Device and PDH device coupling after ethylene total output be 112.52 ten thousand tons/year, 79.90 ten thousand tons/year of propylene yield, integrated apparatus
64.81 hundred million yuans of engineering construction investment.Compared with [comparative example 2], integration transformation after 54.60 ten thousand tons of propylene enhancing/
Year, ethylene yield increases by 2.29%, and propylene yield increases by 215.8%, and engineering is saved in propylene/ethylene product quality ratio=0.71
7.87 hundred million yuans of construction investment, it is equivalent to investment reduction 10.83%, reduces about 1.8 hectares of occupied area.Embodiment 2 is set
The variation of standby load and 2 machine utilization of comparative example is shown in Table 2.
2 machine utilization of table promotes list
[comparative example 3]
The ethylene unit that 1,000,000 tons/year of nominal capacity, using front-end deethanization separation process, cracking stock by 40% ethane,
30% propane, 30% butane composition, propylene/ethylene ratio=0.23,100.00 ten thousand tons/year of ethylene product yield, propylene product produces
Measure 23.00 ten thousand tons/year, 243.71 ten thousand tons/year of cracking stock consumption.
[embodiment 3]
60 tons/year of PDH device nominal capacity, 2.52 ten thousand tons/year of ethylene yield, 54.60 ten thousand tons/year of propylene yield.Ethylene
Device and PDH device coupling after ethylene total output be 102.52 ten thousand tons/year, 77.60 tons/year of propylene yield, integrated apparatus
61.64 hundred million yuans of engineering construction investment.Compared with [comparative example 3], 54.60 ten thousand tons/year of propylene enhancing after integration transformation,
Ethylene yield increases by 2.52%, and propylene yield increases by 237.4%, and engineering construction is saved in propylene/ethylene product quality ratio=0.76
6.07 hundred million yuans are invested, investment reduction 8.96% is equivalent to, reduces about 1.8 hectares of occupied area.3 machine utilization of embodiment
With the variation of 3 machine utilization of comparative example, it is shown in Table 3.
3 machine utilization of table promotes list
[comparative example 4]
The ethylene unit that 800,000 tons/year of nominal capacity, using front-end deethanization separation process, cracking stock by 40% ethane,
30% propane, 30% butane composition, propylene/ethylene ratio=0.23,80.00 ten thousand tons/year of ethylene product yield, propylene product yield
18.40 ten thousand tons/year, 194.97 ten thousand tons/year of cracking stock consumption.
[embodiment 4]
60 tons/year of PDH device nominal capacity, 2.52 ten thousand tons/year of ethylene yield, 54.60 ten thousand tons/year of propylene yield.Ethylene
Device and PDH device coupling after ethylene total output be 82.52 ten thousand tons/year, 73.00 ten thousand tons/year of propylene yield, integrated apparatus
57.21 hundred million yuans of engineering construction investment.Compared with [comparative example 4], 54.60 ten thousand tons/year of propylene enhancing after integration transformation,
Ethylene yield increases by 3.15%, and propylene yield increases by 296.7%, and engineering construction is saved in propylene/ethylene product quality ratio=0.88
4.64 hundred million yuans are invested, investment reduction 7.50% is equivalent to, reduces about 1.8 hectares of occupied area.4 machine utilization of embodiment
With the variation of 4 machine utilization of comparative example, it is shown in Table 4.
4 machine utilization of table promotes list
Comparative example and embodiment summarize, and are shown in Table 5.
5 comparative example of table and embodiment summary sheet
Ethylene unit front-end deethanization point is leveraged fully on from can be seen that PDH device separation equipment in the present invention in 7 data of table
From process, product structure after improving ethylene unit cracking stock lighting improves propylene yield, saves engineering throwing
Money, reduces occupied area, achieves preferable technical effect and economic benefit.
Claims (7)
1. a kind of method that light hydrocarbon cracking front-end deethanization technique is coupled with PDH technique, comprising: (1) ethylene unit: light hydrocarbon cracking is former
Expect cracking reaction occurs in pyrolysis furnace to generate include ethylene, propylene cracking gas, cracking gas is through over-quenching, compression, alkali cleaning, dry
Merge after dry, deep cooling with PDH device product gas, into rectifying separation system；(2) PDH device: raw material propane with come from de-oiling tower
The recycled propane at tower top and propylene rectification tower bottom gasifies in propane gasification tank, and the discharging of gasification tank gas phase is heated in heating furnace
Dehydrogenation reaction temperature, into dehydrogenation reactor, dehydrogenation product gas send to ethylene unit rectifying and separates after compression, drying, deep cooling
System, gasification tank bottom liquid phases enter the recycling of de-oiling tower, and overhead condensation liquid returns to propane gasification tank, C4 and C4 or more the group of tower reactor
It sends to ethylene unit debutanizing tower；(3) coupling device: ethylene cracking gas and PDH device product gas enter dethanizer,
Tower top isolates C2 and C2 following components, and into domethanizing column, tower bottom isolates C3 and C3 or more component, into depropanization
Tower；Demethanation tower top is isolated methane hydrogen byproduct and is sent out out-of-bounds, and tower bottom isolates C2 component, into ethylene rectifying column；Ethylene
Rectifying tower top is isolated ethylene product and is sent out out-of-bounds, and tower bottom isolates ethane, is recycled back into ethylene unit cracking unit；Depropanization
Tower top isolates C3 component, and into propylene rectification tower, tower bottom isolates C4 and C4 or more component, with PDH device de-oiling tower tower bottom
Logistics mixing, into debutanizing tower；Propylene is isolated on propylene rectification tower top, is sent out out-of-bounds as product, and tower bottom isolates propane,
It is recycled back into PDH device propane gasification tank；Depropanization materials at bottom of tower and de-oiling materials at bottom of tower are mixed into debutanizing tower, tower top essence
Fraction separates out C4 component, sends out out-of-bounds as product, tower bottom isolates C5 and C5 or more component, splits with what quenching unit was isolated
It solves gasoline and merges submitting out-of-bounds.
2. the method that light hydrocarbon cracking front-end deethanization technique is coupled with PDH technique according to claim 1, it is characterised in that ethylene
Device nominal capacity: 80~1,200,000 tons/year, cracking stock lighter hydrocarbons are made of 40% ethane, 30% propane, 30% butane, coupling
Device product propylene/ethylene mass ratio P/E=0.23.
3. the method that light hydrocarbon cracking front-end deethanization technique is coupled with PDH technique according to claim 1, it is characterised in that PDH
Device nominal capacity: 600,000 tons/year.
4. the method that light hydrocarbon cracking front-end deethanization technique is coupled with PDH technique according to claim 1, it is characterised in that ethylene
The operating condition of device pyrolysis furnace are as follows: 0.10~0.25MPaA of reaction pressure, 810~870 DEG C of reaction temperature.
5. the method that light hydrocarbon cracking front-end deethanization technique is coupled with PDH technique according to claim 1, it is characterised in that PDH
The operating condition of device reaction device are as follows: 0.10~0.35MPaA of reaction pressure, 500~700 DEG C of reaction temperature.
6. the method that light hydrocarbon cracking front-end deethanization technique is coupled with PDH technique according to claim 1, it is characterised in that rectifying
Separation system carries out rectifying separation to cracking gas and product gas using front-end deethanization route.
7. the method that light hydrocarbon cracking front-end deethanization technique is coupled with PDH technique according to claim 1, it is characterised in that sufficiently
Ethylene unit existing equipment is relied on to be separated, ethylene unit equipment component produce load is opposite to be improved, but PDH device makes
Equipment is reduced, and eliminates dethanizer, cold box system, propylene rectification tower, propylene rectification tower charging desulfurization bed, ethylene refrigeration
Compressor, propylene refrigeration compressor.
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| CN112209794A (en) * | 2020-11-13 | 2021-01-12 | 洛阳智达石化工程有限公司 | System and method for producing propylene by combining light hydrocarbon modification and propane dehydrogenation |
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