CN109722297A - A kind of catalytic reforming process system and process - Google Patents
A kind of catalytic reforming process system and process Download PDFInfo
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- CN109722297A CN109722297A CN201711027211.4A CN201711027211A CN109722297A CN 109722297 A CN109722297 A CN 109722297A CN 201711027211 A CN201711027211 A CN 201711027211A CN 109722297 A CN109722297 A CN 109722297A
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Abstract
A kind of catalytic reforming process system and process, the process system include pre- hydroforming coupled system, prefractionation system and systems stabilisation；It couples pre-hydrotreating reaction and reforming reaction in a membrane reactor, membrane reactor is divided into multiple regions, is respectively completed the separation of pre-hydrotreating reaction, reforming reaction and hydrogen.Catalytic reforming is carried out using process system of the invention, reforming reaction can be made to utilize the heat of hydrogenation reaction, the consumption of energy is greatly saved；And using the specific by pre-hydrotreating reaction product H of film2With the H of the isolated purity is high from system of the recycle hydrogen in reformate2, directly recycled and recycled.
Description
Technical field
The present invention relates to a kind of catalytic reforming process, in particular to a kind of technique for coupling pre-add hydrogen and catalytic reforming.
Background technique
Catalytic reforming process is as the production industrial chemicals such as high-knock rating gasoline blend component and benzene,toluene,xylene
Important oil refining process is the important process in oil refining and petrochemical industry.A large amount of hydrogen of catalytic reforming by-product are to mention again
High oil quality, development plus hydrogen industry provide a large amount of cheap hydrogen sources.Increasingly stringent with various environmental regulations, market is to petroleum
The demand of chemical products is continuously increased and factors, the catalytic reformings such as the cheap hydrogen source of the development need of hydrogenation technique offer are mesh
One of preceding most important oil refining processing technology.
Catalytic reforming unit presses catalyst regeneration mode, can be divided mainly into semi-regenerative reforming, circular regeneration formula weight at present
Whole and continuous regenerative reforming.Three kinds of catalytic reforming units are respectively different because having the characteristics that, press its different original by each refinery
Expect processing request and selects.Semi-regenerative reforming is since plant investment is small, flexible operation, and operating cost is low；Circular regeneration formula weight
Whole technique is equipped with a catalyst regeneration system in semi regeneration reforming process, can successively regenerate the catalysis in each reactor
Agent, the catalyst in each reactor can individually be regenerated at any time by switching out in reaction system；Work is reformed in cyclic regeneration
In skill, ad hoc to have a catalyst regenerator, under CONTINUOUS REFORMER normal operating condition, catalyst is in reactor and regenerator
Between flow, the reclaimable catalyst reacted is sent to be regenerated into regenerator, and the catalyst after regeneration is back to reactor.
Catalytic reforming process catalyst is more harsh to ingredient requirement, therefore needs in reforming process by pre-add hydrogen, in advance
Light component by impurity (S, N, O, the alkene and metal) removal in raw material and is separated (i.e. plug) by fractional distillation process, is reformer
Qualified charging is provided.Material through reforming reactor enters separator and isolates hydrogen-rich recycle, and gained liquid is by stabilizer
It is used as Reformed Gasoline after sloughing light component, is high octane gasoline component (90 or more research octane number (RON)), or is sent to aromatic hydrocarbons pumping
Mention device production aromatic hydrocarbons.
CN105349181A discloses a kind of hydro carbons continuous reforming process: two reforming reactor groups of setting and a regeneration
Device, reaction feed are that series connection carries out relative to the conveying of each reactor in each reforming reactor group；And catalyst exists
The circulation conveying between conveying and reactor group and regenerator between each reactor group be it is in parallel carry out, but catalyst
Conveying in the first reforming reactor group and the second reforming reactor group is all that series connection carries out.
CN102277190A discloses a kind of new catalytic reforming process in by least part stream in the catalyst reduction area
Object is recycled to out can may loop to first instead to raw material preheating charging/effluent exchanger entrance, another part
The top of device is answered, and the gas from the recycle compressor is recycled to the top of the concatenated penultimate reactor.
CN102051230A discloses a kind of process of producing aromatic hydrocarbon by moving bed continuous reforming, and catalytic reforming is using shifting
Dynamic bed CONTINUOUS REFORMER technology, is arranged four reaction areas, reaction raw materials pass sequentially through four reaction areas, from the 4th reaction zone reaction stream
Isolate aromatic hydrocarbon product in object out, the catalyst of the 4th reaction zone discharge is regenerated, and the catalyst after regeneration respectively enters the
One reaction zone and the 4th reaction zone.
CN102002389A is disclosed a kind of to be reformed with side line diced system and the naphtha productive aromatic hydrocarbon of recovery system
System and method, reaction unit are divided into two parts, and the first and/or second reaction unit passes through high-pressure separation apparatus, stabilizer
System, extraction system and diced system of raffinating oil connection, extraction system are also connected with recovery system, diced system of raffinating oil
It is connected with side line Cutting Tap, side line Cutting Tap is connect with third and/or the 4th reaction unit again.
Hydrogenation reaction is exothermic reaction, and reforming reaction is the endothermic reaction.In traditional process flow, raw material pre-add hydrogen is anti-
The heat that should be released does not recycle, and the heat that reforming reaction needs is provided by heating furnace burning fuel completely.And with emphatically
The concentration of the progress of whole reaction, reaction product increases, and conditioned response is carried out to positive direction, more severe to improve reaction rate needs
The reaction condition at quarter, so that energy consumption be made to improve.Meanwhile reaction product through air-cooled or water cooling carries out gas-liquid in traditional process flow
Separation, it is subsequent and increase oil product temperature, it so repeats cooling-heating process and not only consumes largely to cool down load,
Increase the heating energy consumption of down stream train.
Summary of the invention
For existing for catalytic reforming process in the prior art not by the thermal energy of hydrogenation reaction and reforming reaction couple,
Energy dissipation is caused, and in reforming reaction, reaction product concentration increase causes to restrict forward reaction, reduces reaction rate etc. and asks
Topic, the present invention is quasi- to provide a kind of energy-saving catalytic reforming process, couples a reactor for hydrogenation reaction and reforming reaction, with
Membrane reactor combines, the H that the reforming reaction stage is generated2Separation in time promotes the timely progress of reforming reaction, and in reaction work
Heat exchanger is made full use of in skill, reduces energy consumption required for each reaction feed heating and product cooling.
To realize the above-mentioned technical purpose, the present invention uses following technological means:
The technical purpose of first aspect present invention is to provide a kind of catalytic reforming process system, including pre- hydroforming coupled systemes
System, prefractionation system and systems stabilisation；
The pre- hydroforming coupled system includes a membrane reactor；The membrane reactor is followed successively by the area A, B by center outward
Area, the area C and four, the area D region respectively separate IIth area of hydrogen, pre-hydrotreating reaction area, reforming reaction area and separation Ith area of hydrogen, wherein A
Area is set to the center of membrane reactor, and the area B, the area C and the area D are the ring-shaped area coaxial with the area A, between the area A and the area B, the area C and
Using seperation film as interval between the area D；The seperation film is from the area B to the area A, from the area C to the unidirectional hydrogen permeation membrane in the area D；Film is anti-
The area B of device is answered to export connection fractionating system, the tower bottom discharging of fractionating system feeds the C of connection membrane reactor as reforming reaction
Area；The area C of membrane reactor exports stable connection system；
The fractionating system includes fractionating column；
The systems stabilisation includes stabilizer.
In above-mentioned process system, the seperation film is Pd-Ag alloy film, to H2With high selectivity；It is preferred that film
The content of middle Ag is 20% ~ 25%, H2Permeability it is higher.
In above-mentioned process system, other material separates of each area to readily conduct heat of membrane reactor, such as stainless steel.
It further include heat-exchange system in above-mentioned process system, the heat-exchange system includes several heat exchangers, realizes system
The heat exchange of middle storeroom.
In above-mentioned process system, the heat-exchange system is specifically included:
Heat exchanger I, two bursts of coupled chargings are respectively the charging of pre-add hydrogen and the area the B discharging of membrane reactor；
Heat exchanger II, two bursts of coupled chargings are respectively that the area the C discharging of membrane reactor and the tower bottom of fractionating column discharge；
Heat exchanger III, two bursts of coupled chargings are respectively that the area the B discharging of membrane reactor and the tower bottom of fractionating column discharge；
Heat exchanger IV, two bursts of coupled chargings are respectively that the area the C discharging of membrane reactor and the tower bottom of stabilizer discharge.
It further include necessary heating furnace and compressor in above-mentioned process system.
In above-mentioned process system, further, the membrane reactor is fixed bed reactors or moving-burden bed reactor.
In above-mentioned process system, further, the discharging in the area membrane reactor D and reformation hydrogen charging mixing circulation are anti-to film
Answer the area C of device；The discharging in the area membrane reactor A and pre-add hydrogen feed mixing circulation to the area B of membrane reactor.
The technical purpose of second aspect of the present invention is to provide the process that catalytic reforming is carried out using above-mentioned process system,
The following steps are included:
It is passed through the area B of membrane reactor after feedstock oil and hydrogen mixing after heating furnace as the charging of pre-add hydrogen, discharging is connected to
Fractionating column, the tower bottom discharging of fractionating column are connected to the area C of membrane reactor, and discharging enters stabilizer；Hydrogen in the area membrane reactor C
Enter the area D by seperation film, the hydrogen in the area membrane reactor B enters the area A by seperation film, and hydrogen is separated.
In process above method, H is connected to by the isolated hydrogen in the area D of membrane reactor2Surge tank, part are discharged
It collects, is partially mixed after compressor with the discharging of fractionation column bottom, enter film reaction as catalytic reforming feedstock after heated stove heating
The area C of device.
In process above method, the isolated hydrogen in the area A of membrane reactor be recycled to after compressor pre-add hydrogen into
Material.
In process above method, the discharging of the area B of membrane reactor after heat exchanger I and the charging heat exchange of pre-add hydrogen, again into
Enter and enter fractionating column after the tower bottom discharging heat exchange of heat exchanger III and fractionating column, the tower bottom discharging of fractionating column first pass through heat exchanger III with
The area the B discharging heat exchange of membrane reactor, enter back into after the area the C discharging heat exchange of heat exchanger II and membrane reactor as reforming reaction into
Material；The area the C discharging of membrane reactor is introduced into the tower bottom discharging heat exchange of heat exchanger II and fractionating column, enters back into heat exchanger IV and stablize
Enter stabilizer after the tower bottom discharging heat exchange of tower.
In process above method, it will be apparent to a skilled person that the area B and the area C of membrane reactor fill respectively
Fill out catalyst for pre-hydrogenation and reforming catalyst, the catalyst for pre-hydrogenation is cobalt molybdate, nickel molybdate or composite tungsten nickel-cobalt catalyst,
Reaction condition are as follows: 150~300 DEG C of temperature, 1.8~3.0MPa of pressure, hydrogen-oil ratio (volume ratio, standard state) 100 ~ 200, air speed
4~10h-1.The reforming reaction catalyst is platinum-rhenium catalyst and platinum-tin catalyst, and reactor inlet temperature is 480 ~ 520 DEG C,
Platinum-rhenium catalyst is used for fixed bed reactors, reaction condition are as follows: and 1.5 ~ 2MPa of pressure, hydrogen-oil ratio (volume ratio) they are 1000 ~ 1400,
Air speed (volume space velocity) 1.5 ~ 2h-1；Platinum-tin catalyst is used for moving-burden bed reactor, reaction condition are as follows: 0.35 ~ 1.5MPa of pressure,
Hydrogen-oil ratio (molar ratio) is 3 ~ 5,1 ~ 2h of volume space velocity-1.Feedstock oil includes but is not limited to the straight-run naphtha plus hydrogen of low octane rating
Naphtha etc..
Compared with prior art, the present invention has the advantage that
(1) present invention couples pre-add hydrogen and reforming reaction in a reactor, and reforming reaction can make full use of pre-add hydrogen
The heat released is reacted, insufficient heat can be provided from the external world, and the consumption of energy is greatly saved.
(2) pre-add hydrogen and reforming reaction are combined with membrane reactor, utilizes the specific by pre-hydrotreating reaction product of film
H2With the H of the isolated purity is high from system of the recycle hydrogen in reformate2, product H2Promote from the timely separation in system
The positive of main reaction carries out, obtained H2It is directly recycled without carrying out other lock out operation.
(3) heat exchanger is made full use of in technique and method of the invention, realizes that the material of reaction system carries out taking hot heat exchange,
Reduce the thermal energy consumption of system entirety.
Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.
Detailed description of the invention
Catalytic reforming process system schematic Fig. 1 of the invention；
Wherein, 101. membrane reactor, the area 102.A, the area 103.B, the area 104.C, the area 105.D, 201. fractionating columns, 301. stabilizers,
401. heat exchanger Is, 402. heat exchanger IIs, 403. heat exchangers III, 404. heat exchangers IV, 501. heating furnaces I, 502. heating furnaces II,
503. compressors I, 504. compressors II, 505. hydrogen gas buffers.
Specific embodiment
Following non-limiting embodiments can with a person of ordinary skill in the art will more fully understand the present invention, but not with
Any mode limits the present invention.
Embodiment 1
A kind of catalytic reforming process system, including pre- hydroforming coupled system, prefractionation system, systems stabilisation and heat exchange system
System, as shown in Figure 1:
Pre- hydroforming coupled system includes membrane reactor 101, and the membrane reactor is followed successively by the area A 102, the area B by center outward
103, the area C 104 and 105 4, the area D region, respectively separation IIth area of hydrogen, pre-hydrotreating reaction area, reforming reaction area and separation hydrogen I
Area, wherein the area A 102 is set to the center of membrane reactor, and the area B 103, the area C 104 and the area D 105 are the ring-type coaxial with the area A 102
Area, between the area A 102 and the area B 103, between the area C 104 and the area D 105 using seperation film as interval；The seperation film is served as reasons
The area B 103 is to the area A 102, from the area C 104 to the unidirectional hydrogen permeation membrane in the area D 105；
The fractionating column 201 of the outlet of the area B 103 connection fractionating system, the tower bottom discharging of fractionating system is as reforming reaction charging connection C
Area 104, the area C 104 export the stabilizer 301 of stable connection system；
Heat-exchange system includes heat exchanger I 401, heat exchanger II 402, heat exchanger III 403 and heat exchanger IV 404.With heat exchanger I 401
Two bursts of connected chargings are respectively that the charging of pre-add hydrogen and the area B 103 discharge, and two bursts of chargings being connected with heat exchanger II 402 are respectively C
The tower bottom of the discharging of area 104 and fractionating column 201 discharges, be connected with heat exchanger III 403 two bursts chargings be respectively the area B 103 discharge and
The tower bottom of fractionating column 201 discharges, and two bursts of chargings being connected with heat exchanger IV 404 are respectively the discharging of the area C 104 and stabilizer 301
Tower bottom discharging.
In addition, the discharging hydrogen in the area D 105 is recycled to the area C 104 as supplement hydrogen, the discharging hydrogen in the area A 102 is recycled to the area B 103.
In above-mentioned process system, necessary heating furnace and compressor are also set up, wherein heating furnace I 501 is set to pre-add hydrogen
Between charging and membrane reactor 101, heating furnace II 502 is set between catalytic reforming feedstock and membrane reactor 101, and compressor I 503 is set
It is placed between the discharging of the area A 102 and the charging of pre-add hydrogen, compressor II 504 is set between the discharging of the area D 105 and catalytic reforming feedstock, compression
A hydrogen gas buffer 505 is also set up before machine II 504.
In above-mentioned process system, the hydrogen separation membrane in reactor is Pd-Ag alloy film, and wherein the content of Ag is 20%.Reaction
Other of device are interregional using stainless steel material as interval.
Embodiment 2
The process of catalytic reforming is carried out using process above system, comprising the following steps:
Heat exchanger I 401 is first passed through as the charging of pre-add hydrogen after feedstock oil and hydrogen mixing, using being passed through film after heating furnace I 501
The area B 103 of reactor 101, carries out pre-hydrotreating reaction, and feedstock oil carries out hydrofining reaction under the action of catalyst and hydrogen
Organic sulfur, nitrogen compound and the metal impurities etc. in raw material are removed, pre-hydrotreating reaction product discharges from the area B 103, first passes through heat exchange
Device I 401, using heat exchanger III 403 after, be passed through fractionating column 201, the overhead product of fractionating column 201 is H2O、H2S、NH3, lighter hydrocarbons
And tops, tower bottom product discharging first pass through heat exchanger III 403, after being mixed with recycle hydrogen, using heat exchanger II 402, later
It is heated to being passed through the area C 104 of membrane reactor 101 after reaction temperature as catalytic reforming feedstock by heating furnace II 502, reform anti-
It answers, reforming reaction is the endothermic reaction, and heat is provided by the heat that pre-hydrotreating reaction is released；It, which discharges, successively passes through heat exchanger II
402, heat exchanger IV 404 enters stabilizer 301, and overhead product is liquefied petroleum gas, and tower bottom product is to reform stable gasoline, reforms
Stable gasoline can be used as the blend component of high-knock rating gasoline, or further processing production aromatic hydrocarbon product.In pre-hydrotreating reaction
Hydrogen enters the area A 102 by 103 Selective Separation of the area B, and discharging hydrogen is used as supplement hydrogen and pre-add hydrogen after compressing by compressor I 503
Charging mixing can also introduce supplement hydrogen when amounts of hydrogen deficiency from the external world；Hydrogen in reforming reaction is by 104 Selective Separation of the area C
Into the area D 105, hydrogen gas buffer 505 is passed through after discharging, a part discharge is collected, and a part first passes through the compression of compressor II 504
It is mixed afterwards as supplement hydrogen with the discharging of 201 tower bottom of fractionating column and is passed through membrane reactor 101 as reformation hydrogen charging.
In above-mentioned process, membrane reactor 101 is fixed bed reactors, and catalyst for pre-hydrogenation is that composite tungsten nickel cobalt is urged
Agent, reaction condition are 290 DEG C of temperature, pressure 2.2MPa, hydrogen-oil ratio (volume ratio, standard state) 120, air speed 6h-1.It reforms anti-
Answering catalyst is platinum-rhenium catalyst, and reaction condition is 500 DEG C of reactor inlet temperature, pressure 1.9MPa, hydrogen-oil ratio (volume ratio)
It is 1200, air speed (volume space velocity) 1.7h-1。
Claims (12)
1. a kind of catalytic reforming process system, including pre- hydroforming coupled system, prefractionation system and systems stabilisation；
The pre- hydroforming coupled system includes a membrane reactor；The membrane reactor is followed successively by the area A, B by center outward
Area, the area C and four, the area D region respectively separate IIth area of hydrogen, pre-hydrotreating reaction area, reforming reaction area and separation Ith area of hydrogen, wherein A
Area is set to the center of membrane reactor, and the area B, the area C and the area D are the ring-shaped area coaxial with the area A, between the area A and the area B, the area C and
Using seperation film as interval between the area D；The seperation film is from the area B to the area A, from the area C to the unidirectional hydrogen permeation membrane in the area D；Film is anti-
The area B of device is answered to export connection fractionating system, the tower bottom discharging of fractionating system feeds the C of connection membrane reactor as reforming reaction
Area；The area C of membrane reactor exports stable connection system；
The fractionating system includes fractionating column；
The systems stabilisation includes stabilizer.
2. process system according to claim 1, which is characterized in that the seperation film is Pd-Ag alloy film.
3. process system according to claim 1, which is characterized in that other materials of each area to readily conduct heat of membrane reactor
Separate.
4. process system according to claim 1, which is characterized in that further include heat-exchange system, the heat-exchange system includes
Several heat exchangers, the heat exchange of storeroom in completion system.
5. process system according to claim 4, which is characterized in that the heat-exchange system specifically includes:
Heat exchanger I, two bursts of coupled chargings are respectively the charging of pre-add hydrogen and the area the B discharging of membrane reactor；
Heat exchanger II, two bursts of coupled chargings are respectively that the area the C discharging of membrane reactor and the tower bottom of fractionating column discharge；
Heat exchanger III, two bursts of coupled chargings are respectively that the area the B discharging of membrane reactor and the tower bottom of fractionating column discharge；
Heat exchanger IV, two bursts of coupled chargings are respectively that the area the C discharging of membrane reactor and the tower bottom of stabilizer discharge.
6. process system according to claim 1, which is characterized in that the discharging and reformation hydrogen charging in the area membrane reactor D are mixed
Close the area C for being recycled to membrane reactor；The discharging in the area membrane reactor A and pre-add hydrogen feed mixing circulation to the area B of membrane reactor.
7. carrying out the process of catalytic reforming, including following step using process system described in claim 1 ~ 6 any one
It is rapid: to be passed through after heating furnace the area B of membrane reactor after feedstock oil and hydrogen mixing as the charging of pre-add hydrogen, discharging is connected to point
Tower is evaporated, the tower bottom discharging of fractionating column is connected to the area C of membrane reactor, and discharging enters stabilizer；Hydrogen in the area membrane reactor C is logical
It crosses seperation film and enters the area D, the hydrogen in the area membrane reactor B enters the area A by seperation film, and hydrogen is separated.
8. process according to claim 7, which is characterized in that connected by the isolated hydrogen in the area D of membrane reactor
It is connected to H2Surge tank, part discharge are collected, and are partially mixed after compressor with the discharging of fractionation column bottom, are made after heated stove heating
Enter the area C of membrane reactor for catalytic reforming feedstock.
9. process according to claim 7, which is characterized in that the isolated hydrogen in the area A of membrane reactor is through pressing
The charging of pre-add hydrogen is recycled to after contracting machine.
10. process according to claim 7, which is characterized in that the discharging of the area B of membrane reactor by heat exchanger I with
Enter fractionating column, the tower of fractionating column after the charging heat exchange of pre-add hydrogen, after entering back into heat exchanger III and the tower bottom discharging heat exchange of fractionating column
Bottom discharging first passes through the area the B discharging heat exchange of heat exchanger III and membrane reactor, enters back into the area the C discharging of heat exchanger II and membrane reactor
It is fed after heat exchange as reforming reaction；The area the C discharging of membrane reactor be introduced into heat exchanger II and fractionating column tower bottom discharging heat exchange,
Enter stabilizer after entering back into the tower bottom discharging heat exchange of heat exchanger IV and stabilizer.
11. process according to claim 7, which is characterized in that the area B load catalyst for pre-hydrogenation, selected from cobalt molybdate,
Nickel molybdate or composite tungsten nickel-cobalt catalyst, pre-hydrotreating reaction condition are as follows: 150~300 DEG C of temperature, 1.8~3.0MPa of pressure, hydrogen oil
Volume ratio 100 ~ 200,4 ~ 10h of air speed-1。
12. process according to claim 7, which is characterized in that reforming catalyst is loaded in the area C, is catalyzed selected from platinum rhenium
Agent or platinum-tin catalyst, reactor inlet temperature are 480 ~ 520 DEG C, the reaction condition of platinum-rhenium catalyst are as follows: 1.5 ~ 2MPa of pressure,
Hydrogen to oil volume ratio is 1000 ~ 1400,1.5 ~ 2h of volume space velocity-1；The reaction condition of platinum-tin catalyst are as follows: 0.35 ~ 1.5MPa of pressure,
Hydrogen/oil mol ratio is 3 ~ 5,1 ~ 2h of volume space velocity-1。
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| CN110776947A (en) * | 2019-11-15 | 2020-02-11 | 中国石油化工股份有限公司 | Catalytic reforming energy-saving system, energy-saving method and catalytic reforming reaction system |
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Effective date of registration: 20230829 Address after: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Patentee after: CHINA PETROLEUM & CHEMICAL Corp. Patentee after: Sinopec (Dalian) Petrochemical Research Institute Co.,Ltd. Address before: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Patentee before: CHINA PETROLEUM & CHEMICAL Corp. Patentee before: DALIAN RESEARCH INSTITUTE OF PETROLEUM AND PETROCHEMICALS, SINOPEC Corp. |