CN115991631A - Method for producing hydrogenated terphenyl, reaction system, multi-section composite reactor and hydrogenated terphenyl obtained by same - Google Patents
Method for producing hydrogenated terphenyl, reaction system, multi-section composite reactor and hydrogenated terphenyl obtained by same Download PDFInfo
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- 238000006243 chemical reaction Methods 0.000 title claims abstract description 109
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 239000002131 composite material Substances 0.000 title claims abstract description 13
- 238000004519 manufacturing process Methods 0.000 title abstract description 12
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 126
- 239000001257 hydrogen Substances 0.000 claims abstract description 100
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 100
- 239000003054 catalyst Substances 0.000 claims abstract description 85
- 238000000034 method Methods 0.000 claims abstract description 24
- 238000007599 discharging Methods 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims description 86
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 80
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 69
- 235000010290 biphenyl Nutrition 0.000 claims description 35
- 239000004305 biphenyl Substances 0.000 claims description 35
- 238000011068 loading method Methods 0.000 claims description 29
- 230000029936 alkylation Effects 0.000 claims description 24
- 238000005804 alkylation reaction Methods 0.000 claims description 24
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 22
- 239000000463 material Substances 0.000 claims description 22
- 150000002431 hydrogen Chemical class 0.000 claims description 19
- 238000002156 mixing Methods 0.000 claims description 18
- 101100134058 Caenorhabditis elegans nth-1 gene Proteins 0.000 claims description 6
- 239000000047 product Substances 0.000 claims description 6
- 239000007809 chemical reaction catalyst Substances 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 35
- 239000000203 mixture Substances 0.000 description 22
- 238000005984 hydrogenation reaction Methods 0.000 description 9
- 238000012856 packing Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 238000004821 distillation Methods 0.000 description 5
- HHNHBFLGXIUXCM-GFCCVEGCSA-N cyclohexylbenzene Chemical compound [CH]1CCCC[C@@H]1C1=CC=CC=C1 HHNHBFLGXIUXCM-GFCCVEGCSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OIAQMFOKAXHPNH-UHFFFAOYSA-N 1,2-diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC=C1C1=CC=CC=C1 OIAQMFOKAXHPNH-UHFFFAOYSA-N 0.000 description 1
- XJKSTNDFUHDPQJ-UHFFFAOYSA-N 1,4-diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=C(C=2C=CC=CC=2)C=C1 XJKSTNDFUHDPQJ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 229920005591 polysilicon Polymers 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000013341 scale-up Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
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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
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
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Abstract
A process for producing hydrogenated terphenyl, a reaction system, a multi-stage composite reactor, and the resulting hydrogenated terphenyl, the process comprising feeding, reacting, and discharging, the reacting comprising conducting a feed in contact with a catalyst; wherein the reaction comprises n-stage reactions connected in series, catalysts of the reactions in each stage are filled according to gradient, and n is more than or equal to 3; the feeding is divided into n sections, and the n sections respectively enter n sections of reactions; the feed comprises a feedstock and hydrogen, wherein the feedstock comprises benzene. The system and the method for producing the hydrogenated terphenyl can produce the hydrogenated terphenyl with different scales, can adapt to catalysts with different reaction temperatures, and ensure that the selectivity of the hydrogenated terphenyl of each reactor is the same.
Description
Technical Field
The invention relates to the technical field of production of terphenyl, in particular to a method for producing hydrogenated terphenyl, a reaction system, a multi-stage composite reactor and the obtained hydrogenated terphenyl.
Background
The heat conducting oil is also called organic heat carrier, is a heat transfer medium, and has the advantages of uniform heating, accurate temperature control, good heat transfer effect, energy conservation, convenient transportation and operation and the like, so that the heat conducting oil is widely applied to the fields of petroleum and petrochemical industry, chemical fiber industry, polysilicon, aerospace and the like, and the use amount is larger and larger along with wider and wider application. The hydrogenated terphenyl is the best liquid phase high temperature heat conduction oil at present, the hydrogenated terphenyl is obtained by partially hydrogenating the mixture of ortho-terphenyl, meta-terphenyl and para-terphenyl (the saturation is 40%), the hydrogenated terphenyl can be operated at a higher temperature, the flash point is up to 190 ℃, the condensation point is lower than-30 ℃, and the evaporation loss is small. Hydrogenated terphenyl heat transfer oil is currently higher in market price, and currently less research is conducted on the reaction and rectification of hydrogenated terphenyl.
Patent CN103804114a discloses a process for preparing hydrogenated terphenyl, comprising the steps of diphenyl synthesis, first rectification, second rectification, hydrogenation, etc. The invention utilizes a high-performance energy-saving tubular reactor. Wherein the biphenyl synthesis comprises (1) mixing: pure benzene and catalyst are mixed in a circulating tank and then pumped into a benzene evaporator for evaporation; (2) cracking: quantitative benzene steam enters a tubular reactor after being preheated in a heat exchanger, so that the benzene steam reacts in the tubular reactor; (3) and (3) cooling: the reaction gas enters a heat exchanger from a tubular reactor, is cooled after heat exchange, so that gaseous benzene, biphenyl and terphenyl are cooled into liquid, and then is rectified for the first time: putting the benzene and biphenyl liquid into a rectifying kettle, recovering benzene at normal pressure to be used as a synthesis raw material, performing reduced pressure distillation to obtain biphenyl, and rectifying for the second time: and (3) secondarily rectifying residues at the bottom of the rectifying kettle, conveying low-boiling-point substances in the residues into the rectifying kettle to obtain terphenyl, and finally hydrogenating the terphenyl in a hydrogenation autoclave to obtain a hydrogenated terphenyl finished product.
Patent CN111018652a discloses a preparation method of high-purity hydrogenated terphenyl heat-conducting oil, which mainly comprises connecting a reduced pressure distillation tower behind a terphenyl hydrogenation reaction kettle, carrying out chromatographic analysis on a product sample after the terphenyl hydrogenation reaction, determining each component and the content thereof in the product, vacuumizing the reduced pressure distillation tower, self-sucking materials in the hydrogenation reaction kettle into the reduced pressure distillation tower, closing a feed inlet valve after the loading is finished, opening a tower top valve, collecting tower top materials through reduced pressure distillation, cooling the tower top materials through a heat exchanger, and then entering a product storage tank. The preparation of the hydrogenated terphenyl heat conduction oil is carried out by adopting the reaction kettle, and the operation condition and the feeding condition of the reactor are not disclosed.
For large-scale industrial scale-up operations, a reaction system that can produce hydrogenated terphenyl on different scales is highly desirable, approaching practical industrial applications.
Disclosure of Invention
In view of the above problems in the prior art, it is an object of the present invention to provide a method for producing hydrogenated terphenyl, which achieves the production of the target capacity hydrogenated terphenyl by n-stage series reaction operation, and which has the advantage of simple and easily controlled operation.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
a process for producing hydrogenated terphenyl comprising feeding, reacting and discharging, said reacting comprising contacting the feeding with a catalyst; wherein the reaction comprises n-stage reactions connected in series, catalysts of the reactions in each stage are filled according to gradient, and n is more than or equal to 3; the feeding is divided into n sections, and the n sections respectively enter n sections of reactions; the feed comprises a feedstock and hydrogen, wherein the feedstock comprises benzene; preferably a mixture of benzene and at least one of biphenyl and cyclohexane; further preferred is benzene, or a mixture of benzene and biphenyl, or a mixture of benzene, biphenyl and cyclohexane; more preferably a mixture of benzene, biphenyl and cyclohexane, wherein the biphenyl content is preferably not more than 10wt%. Wherein the n-stage feeding is carried out in the 1 st stage and the 2 nd stage … n-stage reactions respectively.
In the technical scheme, the feeding amount of the raw materials entering the 1 st stage reaction is 30-70 wt% of the total feeding amount of the raw materials; the feeding amount of the raw materials entering each reaction section from the 2 nd section to the second last section is 8-16wt% of the total feeding amount of the raw materials; the feed amount of the raw materials entering the final stage reaction is 15-25wt% of the total feed amount of the raw materials.
In the technical scheme, the hydrogen amount entering the 1 st stage reaction is 8-13 wt% of the total hydrogen feeding amount; the hydrogen amount entering each reaction section from the 2 nd section to the second last section is 1.1-1.3 times of the hydrogen amount entering the reaction in the previous section; the hydrogen amount entering the final stage reaction is 1.1-1.45 times of the hydrogen amount entering the penultimate stage reaction.
In the technical scheme, the gradient filling of the reaction catalyst of each section comprises the following steps: the catalyst loading level of each reaction from the 2 nd stage to the second last stage is 1.1-1.3 times of that of the previous reaction; the loading level of the catalyst in the final stage is 1.1-1.45 times of that in the previous stage.
In the technical scheme, the raw material further comprises at least one of biphenyl and cyclohexane; and/or the number of the groups of groups,
the inlet temperature of each reaction section is 140-180 ℃ and the temperature rise is 20-50 ℃; and/or the number of the groups of groups,
the inlet temperature difference of each reaction section is +/-3 ℃, and the temperature difference of each reaction section is +/-3 ℃; and/or the number of the groups of groups,
the reaction pressure of each stage is 300kPa to 800kPa.
It is a second object of the present invention to provide a reaction system for producing hydrogenated terphenyl by the process described, comprising a feed heater, a feed distributor and n hydroalkylation reactors in series.
In the technical scheme, after the raw materials are heated by a feed heater, the raw materials are mixed with hydrogen and then enter a reactor from the top of a first hydroalkylation reactor, and a reaction product is discharged from the reactor and then enters the next hydroalkylation reactor; the discharged material of each hydroalkylation reactor is mixed with the raw material of the next reaction and hydrogen and then enters the reactor from the top of the next hydroalkylation reactor; the resulting hydrogenated terphenyl product is withdrawn from the last hydroalkylation reactor.
In the technical scheme, the raw material feeding amount entering the first hydroalkylation reactor is preferably 35-65 wt% of the total raw material feeding amount; further preferably 40-55wt% of the total raw material feed; the inlet temperature of the first hydroalkylation reactor is controlled by a feed heater, the inlet temperature of the second to n-1 th hydroalkylation reactors is controlled by the feed amount of raw materials entering each of the second to n-1 th hydroalkylation reactors, and the feed amount is 8-16wt% of the total feed amount; preferably 10-15wt% of the total raw material feed; the inlet temperature of the last hydrogenation reactor is controlled by the feed amount of raw materials to the last hydroalkylation reactor, which is 15-25wt% of the total feed amount; preferably 16-22wt% of the total raw material feed.
In the technical scheme, the temperature rise of the first reactor is controlled by the hydrogen amount entering the first hydroalkylation reactor, and is 8% -13% of the total hydrogen amount; preferably 8.5-10 wt% of the total hydrogen; the temperature rise of the second to n-1 hydroalkylation reactors is controlled by the hydrogen amount entering the second to n-1 hydroalkylation reactors, wherein the hydrogen amount entering the second to n-1 hydroalkylation reactors is 1.1 to 1.3 times of the hydrogen amount of the previous reactor; preferably 1.15 to 1.25 times the amount of hydrogen in the previous reaction; the temperature rise of the last hydroalkylation reactor is controlled by the amount of hydrogen entering the last hydroalkylation reactor, which is 1.1-1.45 times the amount of hydrogen entering the penultimate hydroalkylation reactor; preferably 1.15 to 1.4 times.
In the technical scheme, the feeding distributor is arranged at the inlet of each alkylation reactor and is used for discharging a previous hydroalkylation reactor, mixing the raw materials for the reaction with hydrogen and then entering the next hydroalkylation reactor at the top of the reactor.
In the above technical scheme, the catalyst in each alkylation reactor is filled according to the gradient.
It is a further object of the present invention to provide a multistage composite reactor for producing hydrogenated terphenyl by the process described, comprising a feed heater, a hydroalkylation reactor, a reactor feed distributor and an interstage feed distributor; the raw materials and hydrogen are fed in sections; the alkylation reactor comprises n sections of catalyst beds, and the catalyst is filled in a gradient manner. Wherein the raw materials and the hydrogen are fed in sections, namely, the raw materials and the hydrogen are respectively fed on the first bed layer of the reactor, the second bed layer of the reactor, the third bed layer of the reactor … and the n-1 bed layer of the reactor.
In the technical scheme, the feeding heater is arranged outside the reactor and is arranged in front of the inlet of the reactor; the reactor feed distributor is arranged at the inlet in the reactor; the interstage feed distributor is arranged between every two sections of catalyst beds in the reactor.
In the technical scheme, the raw materials are heated by a feeding heater and then enter a reactor and first-stage hydrogen enters a first-stage catalyst bed layer of the reactor after passing through a feeding distributor of a tower top reactor in the reactor; the second-stage raw material of the hydroalkylation reactor, the reaction discharge from the first-stage bed layer and hydrogen enter the second-stage catalyst bed layer of the reactor after passing through a second-stage feeding distributor; similarly, the raw material of the nth-1 section bed layer of the hydroalkylation reactor, the reaction discharge from the nth-2 section bed layer and hydrogen enter the nth-1 section catalyst bed layer of the reactor after passing through an nth-1 section inter-section feeding distributor; the nth section catalyst bed layer of the hydroalkylation reactor is a guard bed to ensure complete reaction of the fed hydrogen.
In the technical scheme, the raw material feeding amount entering the first bed layer of the hydroalkylation reactor is 30-70 wt% of the total raw material feeding amount; further preferably 40-60wt% of the total raw material feed; the inlet temperature of the first bed layer of the reactor is controlled by a feed heater, the inlet temperature of the second bed layer of the reactor to the n-1 bed layer of the reactor is controlled by the feed amount of raw materials entering each section of the second bed layer of the reactor to the n-1 bed layer, and the feed amount of the raw materials is 9-15 wt% of the total feed amount, preferably 10-15wt% of the total feed amount.
In the technical scheme, the temperature rise of the reactor is controlled by the hydrogen amount of each section of bed layer entering the reactor, and the hydrogen amount entering the first section of bed layer is 7-14 wt% of the total hydrogen amount, preferably 8-12 wt% of the total hydrogen amount; the hydrogen amount of each section of bed layers from the second bed layer to the n-2 bed layer of the reactor is 1.05-1.35 times of the hydrogen amount of the previous section; preferably 1.1 to 1.25 times; the amount of hydrogen entering the n-1 bed of the reactor is 1.05-1.45 times of the amount of hydrogen entering the n-2 bed, preferably 1.1-1.4 times of the amount of hydrogen entering the n-2 bed.
In the above reaction, the catalyst loading gradient loading of each section of the bed layer of the reactor comprises: the catalyst loading level of each section of the beds from the second bed to the next to last section is 1.05-1.35 times of the catalyst loading level of the previous section of the beds; preferably 1.15 to 1.25 times; the catalyst loading level of the last section is 1.05-1.45 times of that of the last section; preferably 1.1 to 1.4 times.
It is a fourth object of the present invention to provide a hydrogenated terphenyl produced by the method for producing hydrogenated terphenyl, or by the reaction system for producing hydrogenated terphenyl, or by the reactor.
The invention has the beneficial effects that at least the following 2 aspects are:
firstly, the system for producing hydrogenated terphenyl can produce hydrogenated terphenyl with different scales, can adapt to catalysts with different reaction temperatures, and ensures that the selectivity of hydrogenated terphenyl of each reactor is the same.
Secondly, the raw materials are adopted to control the inlet temperature and the temperature rise of the reactor, so that the energy consumption of the device is low, and a large amount of cost is saved.
Drawings
FIG. 1 is a process flow diagram of the reaction system of example 2;
the reference numerals of fig. 1 are explained as follows: i is a first hydroalkylation reactor; a1 is a first hydroalkylation reactor catalyst; h1 is the catalyst loading height of the first hydroalkylation reactor; II is a second hydroalkylation reactor; a2 is a second hydroalkylation reactor catalyst; h2 is the second hydroalkylation reactor catalyst loading height; III is a third hydroalkylation reactor; a3 is a third hydroalkylation reactor catalyst; h3 is the catalyst loading height of the third hydroalkylation reactor; IV is a fourth hydroalkylation reactor; a4 is a fourth hydroalkylation reactor catalyst; h4 is the catalyst loading height of the fourth hydroalkylation reactor; v is a fifth hydroalkylation reactor; a5 is a fifth hydroalkylation reactor catalyst; h5 is the catalyst loading height of the fifth hydroalkylation reactor; b is a feed heater;
1 is hydrogen from outside the boundary; 2 is the raw material feed; 3 is the feeding of the first hydroalkylation reactor after the heat exchange feeding and the hydrogen are mixed; 4 is the discharge of the first hydroalkylation reactor; 5 is the feeding of a second hydroalkylation reactor after the raw material feeding and the hydrogen are mixed; 6 is the discharge of the second hydroalkylation reactor; 7 is the third hydroalkylation reactor feed after the raw material is mixed with hydrogen, 8 is the third hydroalkylation reactor discharge, 9 is the fourth hydroalkylation reactor feed after the raw material feed is mixed with hydrogen, 10 is the fourth hydroalkylation reactor discharge, and 11-15 are the first through fifth hydroalkylation reactor hydrogen feeds respectively; 16 is the raw material feed, 17 is the fifth hydroalkylation reactor discharge, 18 is the raw material feed which enters the first hydroalkylation reactor after being heated by the heater B, and 21-25 are the raw material feeds of the first to fifth hydroalkylation reactors; c1 C2, C3, C4, C5 are the feed distributors of the first, second, third, fourth, and fifth hydroalkylation reactors, respectively.
FIG. 2 is a process flow diagram of the multi-stage composite reactor of example 4;
the reference numerals of fig. 2 are explained as follows: a is a six-stage hydroalkylation reactor; b is a feed heater; a C feed distributor; D. e, F, G are respectively the second to fifth stage feed distributors of the reactor; A1-A6 are the first to sixth bed catalysts of the hydroalkylation reactor; H1-H6 are the catalyst loading heights of the first to sixth beds;
1 is raw material feeding; 2 is hydrogen from outside the boundary; 3 is the heat carrier feeding of the heat exchanger; 4, discharging the heat carrier of the heater; 5 is the discharge of the hydroalkylation reactor; 21-25 is hydrogen feed; 11-15 are the first to fifth stage feedstock feeds to the hydroalkylation reactor.
Detailed Description
The present invention is described in detail below with reference to specific embodiments, and it should be noted that the following embodiments are only for further description of the present invention and should not be construed as limiting the scope of the present invention, and some insubstantial modifications and adjustments of the present invention by those skilled in the art from the present disclosure are still within the scope of the present invention.
Example 1
Example 1 is a reaction system for producing hydrogenated terphenyl according to the present invention employing four series reactor systems comprising a feed heater, a first hydroalkylation reactor, a second hydroalkylation reactor, a third hydroalkylation reactor, a fourth hydroalkylation reactor, and a reactor feed distributor. The first reactor feed distributor is arranged after the feed heater and before the first alkylation reactor and is used for mixing raw materials with hydrogen and then feeding; the second to fourth reactor feed distributors are arranged between every two hydroalkylation reactors; the catalyst gradient was packed in each reactor bed and the gradient fed to each reactor, the feed amounts being shown in Table 1. Catalyst gradient loading, the catalyst loading height of the first alkylation reactor is 30cm, the catalyst loading height of the second alkylation reactor is 33cm, the catalyst loading height of the third alkylation reactor is 36cm, and the catalyst loading height of the fourth alkylation reactor is 40cm.
Wherein the raw material (mixture of benzene, biphenyl and cyclohexane) is heated by a feed heater and mixed with hydrogen by a reactor feed distributor, enters a first hydroalkylation reactor from the top of the reactor, enters a second hydroalkylation reactor from the top of the reactor after being mixed with hydrogen by the raw material and the discharged material from the first hydroalkylation reactor, enters a third hydroalkylation reactor from the top of the reactor after being mixed with hydrogen by the raw material and the discharged material from the third hydroalkylation reactor, and enters a fourth hydroalkylation reactor from the top of the reactor after being mixed with hydrogen by the raw material and the discharged material from the third hydroalkylation reactor.
The reaction pressure of the reactor is 500kPa, the temperature of the feed hydrogen is 30 ℃, the raw material feed is a mixture of biphenyl, benzene and cyclohexane, the feed temperature is 56 ℃, and the weight percentages of the biphenyl, the benzene and the cyclohexane are as follows: 8%:25%:67%, feed heater outlet temperature 155 ℃.
TABLE 1
Under the conditions of the reaction and the feeding, the inlet temperature of each reactor is controlled at 150 ℃, the temperature of each bed layer of each four-stage reactor is increased by 33 ℃, namely the outlet temperature of each stage reactor is controlled at 183 ℃, so as to exert the optimal efficiency of each reactor, under the conditions, the hydrogen conversion rate is 93%, the cyclohexylbenzene selectivity is 72%, and the hydrogenated terphenyl selectivity is 9%, the system for producing hydrogenated terphenyl can produce hydrogenated terphenyl with different scales, can adapt to catalysts with different reaction temperatures, and ensures that the selectivity of hydrogenated terphenyl of each reactor is the same.
Example 2
Example 2 the reaction process of example 1 and the reaction system similar to that of example 1 were used, the scale was still 1 ten thousand tons/year of hydrogenated terphenyl, except that the benzene and biphenyl as raw materials were reacted in excess in the actual reaction, and since only four reactors and a temperature rise of 33℃were used in example 1, more benzene was circulated, and thus the circulating benzene was higher, and the energy consumption was increased. For this purpose a reaction system comprising 5 reactors as shown in fig. 1 is used, comprising a feed heater B, a first hydroalkylation reactor I, a second hydroalkylation reactor II, a third hydroalkylation reactor III, a fourth hydroalkylation reactor IV, a fifth hydroalkylation reactor V, reactor feed distributors C1, C2, C3, C4 and C5. The reactor feed distributor C1 is arranged after the feed heater B and before the first alkylation reactor I, and is used for mixing raw materials with hydrogen and then feeding; c2 C3, C4 and C5, disposed between each two hydroalkylation reactors; the catalyst gradient was packed in each reactor bed and the gradient fed to each reactor, the feed amounts being shown in Table 2. Catalyst gradient loading, the catalyst loading height of the first alkylation reactor is 20cm, the catalyst loading height of the second alkylation reactor is 22cm, the catalyst loading height of the third alkylation reactor is 24cm, the catalyst loading height of the fourth alkylation reactor is 26cm, and the catalyst loading height of the fifth alkylation reactor is 33cm.
Wherein, raw material 21 is heated by a feeding heater B18 and is mixed with hydrogen 11 by a reactor feeding distributor 3, enters a first hydroalkylation reactor I from the top of the reactor, enters a second hydroalkylation reactor II from the top of the reactor after raw material 22 and a discharging material 4 from the first hydroalkylation reactor are mixed with hydrogen 12, enters a third hydroalkylation reactor III from the top of the reactor after raw material 23 and a discharging material 6 from the second hydroalkylation reactor are mixed with hydrogen 13, enters a fourth hydroalkylation reactor IV from the top of the reactor after raw material 24 and a discharging material 8 from the third hydroalkylation reactor are mixed with hydrogen 14, and enters a fourth hydroalkylation reactor IV from the top of the reactor after raw material 25 and a discharging material 10 from the fourth hydroalkylation reactor are mixed with hydrogen 15 and 16 from the top of the reactor.
The reaction pressure of the reactor is 500kPa, the temperature of the feed hydrogen is 30 ℃, the raw material feed is a mixture of biphenyl, benzene and cyclohexane, the feed temperature is 56 ℃, and the weight percentage of the biphenyl, the benzene and the cyclohexane is as follows: 8%:25%:67%, feed heater outlet temperature 152 ℃.
TABLE 2
Under the above reaction and feeding conditions, the inlet temperature of each reactor is controlled to be 150 ℃, the bed temperature of each stage of five-stage reactors is increased to be 30 ℃, namely the outlet temperature of each stage of reactors is controlled to be 180 ℃, and the optimal efficiency of each reactor can be exerted, under the conditions, the hydrogen conversion rate is 92%, the cyclohexylbenzene selectivity is 70%, and the hydrogenated terphenyl selectivity is 11%. Because 5 reactors are adopted, the feeding amount of benzene and biphenyl is reduced, so that the circulating amount of unreacted benzene and biphenyl is reduced, and the temperature rise of the reactors is also reduced compared with that of the embodiment 1.
Example 3
The method comprises the steps of heating raw materials by a feed heater, mixing the raw materials with hydrogen through a reactor feed distributor, feeding the mixture into a fixed bed hydroalkylation reactor from the top of the reactor, mixing the raw materials with the discharged materials from a first-stage hydroalkylation reactor and the hydrogen, feeding the mixture into a second-stage bed of the hydroalkylation reactor through a second-stage inter-stage feed distributor, mixing the raw materials with the discharged materials from the second-stage hydroalkylation reactor and the hydrogen, feeding the mixture into a third-stage bed of the hydroalkylation reactor through a third-stage inter-stage feed distributor, mixing the raw materials with the discharged materials from the third-stage bed hydroalkylation reactor and the hydrogen, feeding the mixture into a fourth-stage bed of the hydroalkylation reactor through a fourth-stage inter-stage feed mixing distributor, and finally finishing the hydrogenation reaction through a guard bed of the hydroalkylation reactor.
1 ten thousand tons/year hydrogenated terphenyl multistage composite reactor (8000 hours of annual operation), the reaction pressure of the reactor is 500kPa, the temperature of the feed hydrogen is 30 ℃, the raw material feed is a mixture of biphenyl, benzene and cyclohexane, the feed temperature is 56 ℃, and the weight percentages of the biphenyl, the benzene and the cyclohexane are as follows: 8%:25%:67% feed heater outlet temperature 150 ℃.
TABLE 3 Table 3
Under the above reaction and feeding conditions, the inlet temperature of each reactor is controlled to 148 ℃, the temperature rise of each section of the bed layer of the reactor is the same to 31 ℃, namely the outlet temperature of each section of the reactor is controlled to 179 ℃, so as to exert the optimal efficiency of the catalyst of each section of the bed layer of the reactor, and under the conditions, the hydrogen conversion rate is 93%, the cyclohexylbenzene selectivity is 72%, and the hydrogenated terphenyl selectivity is 11%.
Example 4
Example 4 the reactor and reaction process of example 3 was used, which still had a scale of 1 ten thousand tons/year of hydrogenated terphenyl, except that the benzene and biphenyl as the starting materials were excessive in the actual reaction, and that the use of only 148 c for lowering the inlet temperature of the reactor and 31 c for raising the temperature of the bed of each reactor in example 3 resulted in more benzene circulation, and thus too high benzene circulation, and increased energy consumption in operation. For this purpose, a fixed bed reactor as shown in fig. 2 is used, wherein the number of the beds in the reactor is 6, the first 5 layers are reaction beds, and the 6 th layer is a guard bed. The device comprises a feed heater B, a six-section hydroalkylation reactor A, a reactor feed distributor C, a reactor second-section interstage feed distributor D and a reactor third-section interstage feed distributor E; a fourth section of the reactor is provided with a feeding distributor F; the catalysts A1-A6 are packed in a gradient manner, wherein the first five sections are reaction beds, the sixth section is a protective bed, the first section of catalyst is packed at 20cm, the second section of catalyst is packed at 22cm, the third section of catalyst is packed at 24cm, the fourth section of catalyst is packed at 26cm, the fifth section of catalyst is packed at 28cm, the sixth section of protective bed is packed at 35cm, each section of reaction gradient is fed, and the feeding amount is shown in Table 4.
Wherein, the raw material 1 is heated by a feed heater B and is mixed with hydrogen 21 by a reactor feed distributor C, enters a fixed bed hydroalkylation reactor from the top of the reactor, enters a second-stage bed layer of the hydroalkylation reactor by a second-stage inter-stage feed distributor D after being mixed with the discharge from the first-stage bed layer hydroalkylation reactor and hydrogen 22, enters a third-stage bed layer of the hydroalkylation reactor after being mixed with the discharge from the second-stage hydroalkylation reactor and hydrogen 23 by a third-stage inter-stage feed distributor E, enters a fourth-stage bed layer of the hydroalkylation reactor after being mixed with the discharge from the third-stage hydroalkylation reactor and hydrogen 24 by a fourth-stage inter-stage feed mixing distributor F, and finally completes the hydrogenation reaction by a guard bed layer of the hydroalkylation reactor.
The reaction pressure of the reactor is still 500kPa, the temperature of the feed hydrogen is 30 ℃, the raw material feed is a mixture of biphenyl, benzene and cyclohexane, the feed temperature is 56.4 ℃, and the weight percentage of the biphenyl, the benzene and the cyclohexane is as follows: 8%:25%:67%, feed heater outlet temperature 151.7 ℃.
TABLE 4 Table 4
Under the above reaction and feeding conditions, the inlet temperature of each reactor is controlled at 150 ℃, the temperature rise of each section of bed layer of the reactor is controlled at 30 ℃, namely the outlet temperature of each section of reactor is controlled at 180 ℃, and the optimal efficiency of each reactor can be exerted, under the conditions, the hydrogen conversion rate is 95%, the cyclohexylbenzene selectivity is 71%, and the hydrogenated terphenyl selectivity is 12%. Because the composite reactor adopts 5 sections of reaction beds and 1 section of protection beds, the feeding amount of benzene and biphenyl can be reduced, thereby reducing the circulating amount of unreacted benzene and biphenyl, and simultaneously the temperature rise of the reactor is also reduced compared with that of the embodiment 3.
Comparative example 1
In contrast to the reaction system for producing hydrogenated terphenyl of example 1, four series reactor systems were employed, including a feed heater, a first hydroalkylation reactor, a second hydroalkylation reactor, a third hydroalkylation reactor, a fourth hydroalkylation reactor, and a reactor feed distributor. The first reactor feed distributor is arranged after the feed heater and before the first alkylation reactor and is used for mixing raw materials with hydrogen and then feeding; the second to fourth reactor feed distributors are arranged between every two hydroalkylation reactors; each reactor was equally charged with catalyst packed non-gradient and each alkylation reactor was catalyst packed to a height of 33cm.
Wherein the raw materials (the raw materials except benzene and biphenyl and cyclohexane) are heated by a feed heater and mixed with hydrogen by a reactor feed distributor, enter a first hydroalkylation reactor from the top of the reactor, enter a second hydroalkylation reactor from the top of the reactor after the raw materials, the discharged materials from the first hydroalkylation reactor and the hydrogen are mixed, enter a third hydroalkylation reactor from the top of the reactor after the raw materials, the discharged materials from the second hydroalkylation reactor and the hydrogen are mixed, and enter a fourth hydroalkylation reactor from the top of the reactor after the raw materials, the discharged materials from the third hydroalkylation reactor and the hydrogen are mixed.
The reaction pressure of the reactor is 500kPa, the temperature of the feed hydrogen is 30 ℃, the raw material feed is a mixture of biphenyl, benzene and cyclohexane, the feed temperature is 56 ℃, and the weight percentages of the biphenyl, the benzene and the cyclohexane are as follows: 8%:25%:67%, feed heater outlet temperature 155 ℃.
TABLE 5
Under the conditions of the reaction and the feeding, the inlet temperature of the first reactor is controlled at 146 ℃, the temperature of each reactor of the four reactors is raised differently and is respectively at 50 ℃,61 ℃,70 ℃ and 82 ℃, so that the optimal efficiency of each reactor cannot be exerted completely, the optimal reaction temperature which can be tolerated by the catalyst is 180-210 ℃, and the production cannot be carried out normally, thus the effectiveness of the method is verified by the comparative example, and the performance of the catalyst of each reactor can be exerted to the maximum efficiency by the method.
Comparative example 2
The method comprises the steps of adopting a five-stage fixed bed hydroalkylation reactor, wherein the five-stage fixed bed hydroalkylation reactor comprises a reactor feed distributor, a feed heater and a hydroalkylation reactor, wherein the reactor comprises a second-stage feed distributor and a third-stage feed distributor; a fourth section of the reactor is provided with a feeding distributor; the reactor of each section is equally fed, the catalyst is not loaded in a gradient way, the catalyst loading height of each alkylation reactor of each section is 30cm, and the feeding amount is shown in Table 6.
The method comprises the steps of heating raw materials by a feed heater, mixing the raw materials with hydrogen through a reactor feed distributor, feeding the mixture into a fixed bed hydroalkylation reactor from the top of the reactor, mixing the raw materials with the discharged materials from a first-stage hydroalkylation reactor and the hydrogen, feeding the mixture into a second-stage bed of the hydroalkylation reactor through a second-stage inter-stage feed distributor, mixing the raw materials with the discharged materials from the second-stage hydroalkylation reactor and the hydrogen, feeding the mixture into a third-stage bed of the hydroalkylation reactor through a third-stage inter-stage feed distributor, mixing the raw materials with the discharged materials from the third-stage bed hydroalkylation reactor and the hydrogen, feeding the mixture into a fourth-stage bed of the hydroalkylation reactor through a fourth-stage inter-stage feed mixing distributor, and finally finishing the hydrogenation reaction through a guard bed of the hydroalkylation reactor.
1 ten thousand tons/year hydrogenated terphenyl multistage composite reactor (8000 hours of annual operation), the reaction pressure of the reactor is 500kPa, the temperature of the feed hydrogen is 30 ℃, the raw material feed is a mixture of biphenyl, benzene and cyclohexane, the feed temperature is 56 ℃, and the weight percentages of the biphenyl, the benzene and the cyclohexane are as follows: 8%:25%:67% feed heater outlet temperature 150 ℃.
TABLE 6
Under the above reaction and feeding conditions, the inlet temperature of the first section of the reactor is controlled at 148 ℃, the temperature rise of each section of the reactor is different, and the temperature rise of each section of the reactor is respectively at 49 ℃,60 ℃,69 ℃ and 80 ℃, so that the optimal efficiency of each section of the reactor cannot be exerted, the optimal reaction temperature which can be tolerated by the catalyst is completely exceeded by 180 ℃ to 210 ℃, and the production cannot be normally carried out, and the effectiveness of the method is verified by the comparative example, so that the method can exert the maximum efficiency of the catalyst of each section of the reactor.
Comparative example 3
A2 series reactor system was employed comprising a feed heater, a first hydroalkylation reactor, a second hydroalkylation reactor, and a reactor feed distributor. The first reactor feed distributor is arranged after the feed heater and before the first alkylation reactor and is used for mixing raw materials with hydrogen and then feeding; the second reactor feed distributor was set between 2 alkylation reactors, each reactor fed in a gradient, the feed rates being shown in table 7. Catalyst was packed in a gradient, the catalyst packing height of the first alkylation reactor was 65cm and the catalyst packing height of the second alkylation reactor was 75cm.
Wherein, the raw material (mixture of benzene, biphenyl and cyclohexane) is heated by a feed heater and mixed with hydrogen by a reactor feed distributor, then enters a first hydroalkylation reactor from the top of the reactor, and then enters a second hydroalkylation reactor from the top of the reactor after the raw material, the discharged material from the first hydroalkylation reactor and the hydrogen are mixed.
The reaction pressure of the reactor is 500kPa, the temperature of the feed hydrogen is 30 ℃, the raw material feed is a mixture of biphenyl, benzene and cyclohexane, the feed temperature is 56 ℃, and the weight percentages of the biphenyl, the benzene and the cyclohexane are as follows: 8%:25%:67%, feed heater outlet temperature 155 ℃.
TABLE 7
Under the conditions of the reaction and the feeding, the inlet temperature of the first reactor is controlled at 150 ℃, the temperature rise of the first reactor is 42 ℃, the temperature rise of the second reactor is 120 ℃, under the conditions, the optimal efficiency of the catalyst in the reactor bed layer can not be exerted completely, the optimal reaction temperature which can be tolerated by the catalyst is 180-210 ℃, and the production can not be normally carried out, so that the effectiveness of the method is verified by the comparative example, and the maximum efficiency of the method can be exerted on the performance of the catalyst in each section of the reactor.
Claims (13)
1. A process for producing hydrogenated terphenyl comprising feeding, reacting and discharging, said reacting comprising contacting the feeding with a catalyst; wherein the reaction comprises n-stage reactions connected in series, catalysts of the reactions in each stage are filled according to gradient, and n is more than or equal to 3; the feeding is divided into n sections, and the n sections respectively enter n sections of reactions; the feed comprises a feedstock and hydrogen, wherein the feedstock comprises benzene.
2. The process of claim 1 wherein the feedstock feed to the stage 1 reaction is from 30% to 70% by weight of the total feedstock feed; the feeding amount of the raw materials entering each reaction section from the 2 nd section to the second last section is 8-16wt% of the total feeding amount of the raw materials; the feed amount of the raw materials entering the final stage reaction is 15-25wt% of the total feed amount of the raw materials.
3. The process of claim 1 wherein the amount of hydrogen entering the stage 1 reaction is 8% to 13% by weight of the total hydrogen feed; the hydrogen amount entering each reaction section from the 2 nd section to the second last section is 1.1-1.3 times of the hydrogen amount entering the reaction in the previous section; the hydrogen amount entering the final stage reaction is 1.1-1.45 times of the hydrogen amount entering the penultimate stage reaction.
4. The method of claim 1, wherein the gradient loading of each stage of reaction catalyst comprises: the catalyst loading level of each reaction from the 2 nd stage to the second last stage is 1.1-1.3 times of that of the previous reaction; the catalyst loading level of the final stage reaction is 1.1-1.45 times of that of the penultimate stage reaction.
5. The method according to any one of claims 1-4, wherein:
the feedstock further comprises at least one of biphenyl and cyclohexane; and/or the number of the groups of groups,
the inlet temperature of each reaction section is 140-180 ℃ and the temperature rise is 20-50 ℃; and/or the number of the groups of groups,
the inlet temperature difference of each reaction section is +/-3 ℃, and the temperature difference of each reaction section is +/-3 ℃; and/or the number of the groups of groups,
the reaction pressure of each stage is 300kPa to 800kPa.
6. A reaction system for producing hydrogenated terphenyl from the process of any of claims 1-5, comprising a feed heater, a feed distributor, and n hydroalkylation reactors in series.
7. The reaction system of claim 6 wherein the feed is heated by the feed heater and mixed with hydrogen before entering the reactor from the top of the first hydroalkylation reactor and the reaction product is discharged from the reactor before entering the next hydroalkylation reactor; the discharged material of each hydroalkylation reactor is mixed with the raw material of the next reaction and hydrogen and then enters the reactor from the top of the next hydroalkylation reactor; the resulting hydrogenated terphenyl product is withdrawn from the last hydroalkylation reactor.
8. The reaction system of claim 6 wherein said feed distributor is disposed at the inlet to each alkylation reactor for feeding the effluent from the previous hydroalkylation reactor, the feedstock for the present stage reaction, and hydrogen to the present stage reaction hydroalkylation reactor at the top of the reactor after mixing.
9. The reaction system of any one of claims 6 to 8 wherein the catalyst in each alkylation reactor is packed in the gradient.
10. A multistage composite reactor for producing hydrogenated terphenyl from the process of any of claims 1-5 comprising a feed heater, a hydroalkylation reactor, a reactor feed distributor, and an interstage feed distributor; the raw materials and hydrogen are fed in sections; the alkylation reactor comprises n sections of catalyst beds, and each section of catalyst is filled according to the gradient.
11. The multistage composite reactor according to claim 10, wherein the feed heater is disposed outside the reactor, before the reactor inlet; the reactor feed distributor is arranged at the inlet in the reactor; the interstage feed distributor is arranged between every two sections of catalyst beds in the reactor.
12. The multi-stage composite reactor according to claim 10, wherein the feedstock enters the reactor after being heated by the feed heater and enters the reactor with the first stage of hydrogen after passing through the overhead reactor feed distributor in the reactor; the second-stage raw material of the hydroalkylation reactor, the reaction discharge from the first-stage bed layer and hydrogen enter the second-stage catalyst bed layer of the reactor after passing through a second-stage feeding distributor; the raw material of the nth-1 section bed layer of the hydroalkylation reactor, reaction discharge from the nth-2 section bed layer and hydrogen enter the nth-1 section catalyst bed layer of the reactor after passing through an nth-1 section inter-section feed distributor; the nth section catalyst bed layer of the hydroalkylation reactor is a guard bed.
13. A process for producing hydrogenated terphenyl according to any one of claims 1 to 5, or a reaction system for producing hydrogenated terphenyl according to any one of claims 6 to 9, or hydrogenated terphenyl produced by the reactor according to any one of claims 10 to 12.
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