Nothing Special   »   [go: up one dir, main page]

CN106699500A - Production method of phthalic anhydride raw material - Google Patents

Production method of phthalic anhydride raw material Download PDF

Info

Publication number
CN106699500A
CN106699500A CN201510769231.3A CN201510769231A CN106699500A CN 106699500 A CN106699500 A CN 106699500A CN 201510769231 A CN201510769231 A CN 201510769231A CN 106699500 A CN106699500 A CN 106699500A
Authority
CN
China
Prior art keywords
reaction
hydro
accordance
upgrading
catalyst
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201510769231.3A
Other languages
Chinese (zh)
Other versions
CN106699500B (en
Inventor
全辉
张志银
赵威
孙国权
林振发
李莉
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
China Petroleum and Chemical Corp
Sinopec Fushun Research Institute of Petroleum and Petrochemicals
Original Assignee
China Petroleum and Chemical Corp
Sinopec Fushun Research Institute of Petroleum and Petrochemicals
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by China Petroleum and Chemical Corp, Sinopec Fushun Research Institute of Petroleum and Petrochemicals filed Critical China Petroleum and Chemical Corp
Priority to CN201510769231.3A priority Critical patent/CN106699500B/en
Publication of CN106699500A publication Critical patent/CN106699500A/en
Application granted granted Critical
Publication of CN106699500B publication Critical patent/CN106699500B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C7/00—Purification; Separation; Use of additives
    • C07C7/005—Processes comprising at least two steps in series
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/88—Molybdenum
    • B01J23/882—Molybdenum and cobalt
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
    • C07C2523/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
    • C07C2523/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • C07C2523/85—Chromium, molybdenum or tungsten
    • C07C2523/88—Molybdenum
    • C07C2523/882—Molybdenum and cobalt

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Analytical Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Water Supply & Treatment (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention relates to a production method of a phthalic anhydride raw material. The method is characterized in that the raw material for producing phthalic anhydride is produce through sequentially carrying out hydrofinishing, hydrogenation modifying and fractionation on coal tar used as raw oil. Sulfur and nitrides are basically completely removed from the phthalic anhydride production raw material obtained in the invention through the method.

Description

A kind of production method of phthalic anhydride raw material
Technical field
Take specifically coal tar as the method for material combination technique productions phthalic anhydride raw material the present invention relates to a kind of production method of phthalic anhydride raw material.
Background technology
Start the crude naphthalene fluid bed legal system phthalic anhydride developed by BASF Corp. of Germany the eighties in last century, have developed ortho-xylene legal system phthalic anhydride again later, naphthalene method is gradually substituted.Until in recent years, because ortho-xylene price is high, raw material is difficult buying, and industrial naphthalene raw material is sufficient, and price is relatively low, and naphthalene legal system phthalic anhydride technique turns into preferably selection again.The refined purification technique of naphthalene mainly has two major classes:Physical method and chemical method.The former includes crystallisation and rectification method.The latter mainly includes acid treating, hydrofinishing and oxide purification.
CN 1192430A propose a kind of combination process for purification of thick naphthalene, and thick naphthalene first carries out hydrofinishing under 0.1-0.9MPa pressure, and hydrogenation products are fractionated into method or crystallisation and separate naphthane and naphthalene, and naphthane is looped back into hydrogenation reactor entrance, improve the yield of naphthalene.Although the method can obtain the refined naphthalene of purity 99.9%, because hydrogenation pressure is relatively low, in 10ppm or so, nitrogen content will influence the quality of phthalic anhydride product for producing to the sulfur content of refined naphthalene product in 40ppm or so during phthalic anhydride.
The content of the invention
In view of the shortcomings of the prior art, the present invention provides one kind with coal tar as raw material, the method that phthalic anhydride raw material is produced using hydrofinishing-hydro-upgrading-fractionation group technology, raw material sulphur, the nitride substantially all removing obtained using the inventive method.
The present invention provides a kind of production method of phthalic anhydride raw material, and methods described includes following content：
（1）Feedstock oil enters hydrofining reaction area, in the presence of hydrogen and Hydrobon catalyst, carries out hydrofining reaction；
（2）By step（1）The product obtained after reaction carries out gas-liquid separation, isolates the liquid phase after gas into hydro-upgrading reaction zone, in the presence of hydrogen and catalyst for hydro-upgrading, carries out hydro-upgrading reaction；
（3）By step（2）The product for obtaining is fractionated, isolated 187~196 DEG C of cuts and 205 DEG C~220 DEG C cuts, 187~196 DEG C of cuts are looped back into one or two in hydrofining reaction area and hydro-upgrading reaction zone, 205~220 DEG C of cuts are the raw material of production phthalic anhydride.
In the inventive method, step（1）Described in feedstock oil be 215 DEG C~230 DEG C cuts obtained after coal tar fractional distillation.
In the inventive method, step（1）Described in hydrofining reaction area filling Hydrobon catalyst, the active metal component of the Hydrobon catalyst is vib and group VIII metal, and described vib metals are selected from Mo and/or W, and its content is calculated as 10wt%~25wt% with oxide；Group VIII metal is selected from Co and/or Ni, and its content is calculated as 3wt%~7wt% with oxide.Wherein, VIB/（VIB+VIII）Atomic ratio is 0.30~0.70, preferably 0.45~0.50.The Hydrobon catalyst should be vulcanized using procatalyst, it is ensured that hydrogenation active metals are in sulphided state during the course of the reaction.
In the inventive method, step（1）Described in hydrofining reaction area operating condition be：Reaction pressure is 0.5~18.0MPa, preferably 1.0~3.0MPa；Reaction temperature is 230~430 DEG C, preferably 260 DEG C~350 DEG C；Hydrogen to oil volume ratio is 200~1500, preferably 600:1~800:1；Volume space velocity is 0.5~10.0h-1, preferably 1.0h-1~3.0h-1。
In the inventive method, step（2）Described in gas-liquid separating method use the operating condition of flash separation, the flash separation to be：The Mpa of pressure 0.05~0.3,40~200 DEG C of temperature.
In the inventive method, step（2）Described in the catalyst that uses of hydro-upgrading reaction zone use alumina support, partial oxidation silicon or molecular sieve can be also added in carrier；The active metal component of catalyst is one or more in Pt, Pd and Rh, content in the catalyst is 0.1wt%~5.0wt%, selectable adjuvant component is one or more in boron, fluorine, chlorine and phosphorus, and content in the catalyst is 0.1wt%~5.0wt%, preferably 0.1wt%~1.0wt%.；The specific surface of catalyst for hydro-upgrading is 150~500m2/ g, pore volume is 0.15~0.60ml/g.
In the inventive method, step（3）Described in hydro-upgrading reaction zone operating condition be：Reaction pressure is 0.05~3.0MPa, preferably 0.1~1.0MPa；Reaction temperature is 200~550 DEG C, preferably 350 DEG C~500 DEG C；Hydrogen to oil volume ratio is 100~1000, preferably 200:1~400:1；Volume space velocity is 0.1~10.0h-1, preferably 0.5h-1~3.0h-1。
In the inventive method, the reaction temperature of the hydro-upgrading reaction zone is higher than the reaction temperature in hydrofining reaction area 100~200 DEG C, the reaction pressure 1.0~2.0MPa lower than the reaction pressure in hydrofining reaction area of the hydro-upgrading reaction zone.
In the inventive method, step（3）Described in fractionation use the condition of vacuum distillation, the vacuum distillation to be：100~200kpa of distillation tower top pressure, convenient tower top pressure is 120~150 kpa, and destilling tower column bottom temperature is 210 DEG C~260 DEG C.
The inventive method is by the hydrofining technology using specific medium relatively low pressure, ensure the sulphur in feedstock oil, the substantially all removing of nitride, reduce its influence to subsequent production phthalic anhydride raw material as far as possible, by the hydrogenation modifying process using lower pressure and higher reaction temperatures, with reference under catalyst for hydro-upgrading effect, hydrofining reaction product is converted into the raw material for being suitable to produce phthalic anhydride more as far as possible, and inventor has found, 187~196 DEG C of cuts are totally unfavorable to generation phthalic anhydride in generation oil, therefore separated, and it is recycled back one or two in hydrofining reaction area and hydro-upgrading reaction zone, by looping back hydrofining reaction area, its generation is controlled by the chemical balance of aromatic hydrocarbons saturation.Hydro-upgrading reaction zone is looped back, by the way that in low pressure, high temperature under conditions of noble metal catalyst, is further converted to produce the raw material of phthalic anhydride, reduce further this section of yield of cut, improves the yield of phthalic anhydride raw material.
Specific embodiment
The particular content and effect of the inventive method are illustrated below by specific embodiment.
Following implementation row will be further described to the method that the present invention is provided, but scope not thereby limiting the invention.The feedstock oil of present invention treatment is Xinjiang coal tar fraction, and specific nature is shown in Table 1, and the Hydrobon catalyst property of use is shown in Table 2.The catalyst for hydro-upgrading property of use is shown in Table 3.
The raw material oil nature of table 1
The property of the Hydrobon catalyst of table 2
The property of the catalyst for hydro-upgrading of table 3
Embodiment 1
With raw material 1 in table 1 as raw material, 4 are specifically shown in Table using hydrofinishing-hydro-upgrading-fractionation process production phthalic anhydride raw material result, wherein 187~196 DEG C of cuts all loop back hydrofining reaction area in generation oil.
Embodiment 2
With raw material 2 in table 1 as raw material, using hydrofinishing -- the Catalyst Production phthalic anhydride raw material result in hydro-upgrading-fractionation process and table 2 and table 3 is specifically shown in Table 4,187~196 DEG C of cuts loop back hydro-upgrading reaction zone and hydrofining reaction area in wherein generating oil, and circulation ratio is 1:1.
Comparative example 1
It is that 300, hydrogen to oil volume ratio is that 400, volume space velocity is 1.0h in reaction pressure 1.5MPa, reaction temperature from Hydrobon catalyst in table 2 with raw material 1 in table 1 as raw material-1Under conditions of carry out hydrofinishing, through vapor-liquid separation, product liquid continues to be cooled to 15 DEG C -20 DEG C to hydrogenation products, and the crystallization of precipitation is phthalic anhydride raw material, and low pressure hydrofining-crystallization processes production phthalic anhydride raw material result is specifically shown in Table 4.
Comparative example 2
With raw material 2 in table 1 as raw material, using hydrofinishing -- hydrogenation modifying process produces phthalic anhydride raw material, and 187~196 DEG C of cuts do not return to hydrofining reaction area and hydro-upgrading reaction zone in the generation oil, are as a result specifically shown in Table 4.
Table 4 produces phthalic anhydride raw material result

Claims (13)

1. a kind of production method of phthalic anhydride raw material, methods described includes following content：
（1）Feedstock oil enters hydrofining reaction area, in the presence of hydrogen and Hydrobon catalyst, carries out hydrofining reaction；
（2）By step（1）The product obtained after reaction carries out gas-liquid separation, isolates the liquid phase after gas into hydro-upgrading reaction zone, in the presence of hydrogen and catalyst for hydro-upgrading, carries out hydro-upgrading reaction；
（3）By step（2）The product for obtaining is fractionated, isolated 187~196 DEG C of cuts and 205 DEG C~220 DEG C cuts, 187~196 DEG C of cuts are looped back into one or two in hydrofining reaction area and hydro-upgrading reaction zone, 205~220 DEG C of cuts are the raw material of production phthalic anhydride.
2. in accordance with the method for claim 1, it is characterised in that：Step（1）Described in feedstock oil be 215 DEG C~230 DEG C cuts obtained after coal tar fractional distillation.
3. in accordance with the method for claim 1, it is characterised in that：Step（1）Described in the active metal component of Hydrobon catalyst be vib and group VIII metal, described vib metals are selected from Mo and/or W, and its content is calculated as 10wt%~25wt% with oxide；Group VIII metal is selected from Co and/or Ni, and its content is calculated as 3wt%~7wt% with oxide.
4. in accordance with the method for claim 3, it is characterised in that：Step（1）Described in VIB/ in Hydrobon catalyst（VIB+VIII）Atomic ratio is 0.30~0.70, preferably 0.45~0.50.
5. in accordance with the method for claim 1, it is characterised in that：Step（1）Described in hydrofining reaction area operating condition be：Reaction pressure is 0.5~18.0MPa, and reaction temperature is 230~430 DEG C, and hydrogen to oil volume ratio is 200~1500, and volume space velocity is 0.5~10.0h-1, preferably 1.0h-1~3.0h-1。
6. in accordance with the method for claim 5, it is characterised in that：Step（1）Described in hydrofining reaction area operating condition be：Reaction pressure is 1.0~3.0MPa, and reaction temperature is 260 DEG C~350 DEG C, and hydrogen to oil volume ratio is 600:1~800:1, volume space velocity is 1.0h-1~3.0h-1。
7. in accordance with the method for claim 1, it is characterised in that：Step（2）Described in gas-liquid separating method use the operating condition of flash separation, the flash separation to be：The Mpa of pressure 0.05~0.3,40~200 DEG C of temperature.
8. in accordance with the method for claim 1, it is characterised in that：Step（2）Described in the catalyst that uses of hydro-upgrading reaction zone use alumina support, partial oxidation silicon or molecular sieve are added in carrier；The active metal component of catalyst is one or more in Pt, Pd and Rh, content in the catalyst is 0.1wt%~5.0wt%, selectable adjuvant component is one or more in boron, fluorine, chlorine and phosphorus, and content in the catalyst is 0.1wt%~5.0wt%, preferably 0.1wt%~1.0wt%.
9. in accordance with the method for claim 1, it is characterised in that：Step（2）Described in catalyst for hydro-upgrading specific surface be 150~500m2/ g, pore volume is 0.15~0.60ml/g.
10. in accordance with the method for claim 1, it is characterised in that：Step（3）Described in hydro-upgrading reaction zone operating condition be：Reaction pressure is 0.05~3.0MPa, and reaction temperature is 200~550 DEG C, and hydrogen to oil volume ratio is 100~1000, and volume space velocity is 0.1~10.0h-1。
11. in accordance with the method for claim 10, it is characterised in that：Step（3）Described in hydro-upgrading reaction zone operating condition be：Reaction pressure is 0.1~1.0MPa；Reaction temperature is 350 DEG C~500 DEG C；Hydrogen to oil volume ratio is 200:1~400:1；Volume space velocity is 0.5h-1~3.0h-1。
12. in accordance with the method for claim 1, it is characterised in that：The reaction temperature of the hydro-upgrading reaction zone is higher than the reaction temperature in hydrofining reaction area 100~200 DEG C, the reaction pressure 1.0~2.0MPa lower than the reaction pressure in hydrofining reaction area of the hydro-upgrading reaction zone.
13. in accordance with the method for claim 1, it is characterised in that：Step（3）Described in fractionation use the condition of vacuum distillation, the vacuum distillation to be：Distillation 100~200kpa of tower top pressure, destilling tower column bottom temperature is 210 DEG C~260 DEG C.
CN201510769231.3A 2015-11-12 2015-11-12 Production method of phthalic anhydride raw material Active CN106699500B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201510769231.3A CN106699500B (en) 2015-11-12 2015-11-12 Production method of phthalic anhydride raw material

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201510769231.3A CN106699500B (en) 2015-11-12 2015-11-12 Production method of phthalic anhydride raw material

Publications (2)

Publication Number Publication Date
CN106699500A true CN106699500A (en) 2017-05-24
CN106699500B CN106699500B (en) 2020-03-17

Family

ID=58918813

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201510769231.3A Active CN106699500B (en) 2015-11-12 2015-11-12 Production method of phthalic anhydride raw material

Country Status (1)

Country Link
CN (1) CN106699500B (en)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0585960A (en) * 1991-09-27 1993-04-06 Osaka Gas Co Ltd Production of purified naphthalene
CN1192430A (en) * 1997-01-20 1998-09-09 法国石油公司 Process for purifying naphthalene by selective hydrotreatment followed by separation

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0585960A (en) * 1991-09-27 1993-04-06 Osaka Gas Co Ltd Production of purified naphthalene
CN1192430A (en) * 1997-01-20 1998-09-09 法国石油公司 Process for purifying naphthalene by selective hydrotreatment followed by separation

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
赵云发等: "12.6.4 带有物料循环的流程的组合设计", 《化工设计学（上册）》 *

Also Published As

Publication number Publication date
CN106699500B (en) 2020-03-17

Similar Documents

Publication Publication Date Title
KR102655920B1 (en) Epoxidation method of propene
US10100024B2 (en) Process for the epoxidation of an olefin
CN109219598B (en) Integrated process for the preparation of propene and propene oxide from propane
JP2017101025A (en) Precision purification of isophorone nitrile by molten crystallization
JP2017505224A (en) Processing of gas mixtures formed from the product stream of a dimethyl reactor by separation techniques.
JP6889644B2 (en) Oxygen isotope substitution method and oxygen isotope substitution device
WO2017162446A1 (en) Process for the epoxidation of propene
TWI417272B (en) Process
JP4834658B2 (en) Method and apparatus for processing a feedstock containing butadiene
CN109071394B (en) Hydroformylation process
CN106699500A (en) Production method of phthalic anhydride raw material
JP6935282B2 (en) Oxygen isotope substitution method and oxygen isotope substitution device
JP2011506419A5 (en)
WO2013118552A1 (en) Method for producing formaldehyde gas and apparatus for producing formaldehyde gas
TW200806607A (en) Process for the manufacture of primary diamines
KR102364917B1 (en) Purification method of aqueous solution containing diethyl acetal
CN106699708A (en) Production method for phthalic anhydride
JP2008512466A (en) Separation of 6-aminocapronitrile and hexamethylenediamine from a mixture containing hexamethylenediamine, 6-aminocapronitrile and tetrahydroazepine
CN111566078B (en) Comprising selective removal of Cu from butynediol starting material ++ Ionic improved process for the production of butanediol
TWI624302B (en) Heat management process
WO2024099083A1 (en) Production process for crude isocyanate having low single-benzene-ring impurity content
JP7434152B2 (en) Method for removing dienes from a stream containing C3-C5 hydrocarbons by selective hydrogenation
TW202246199A (en) Method for producing propylene
JP2005501119A (en) Improved head column operation in acrylonitrile production.
KR101573581B1 (en) Process ofr the removal of olefin component from c3 lpg

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant