CN116986995A - Method for separating and purifying 1, 2-cyclohexanediamine from product of hexanediamine hydrogenation synthesis from adiponitrile - Google Patents
Method for separating and purifying 1, 2-cyclohexanediamine from product of hexanediamine hydrogenation synthesis from adiponitrile Download PDFInfo
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- CN116986995A CN116986995A CN202310925732.0A CN202310925732A CN116986995A CN 116986995 A CN116986995 A CN 116986995A CN 202310925732 A CN202310925732 A CN 202310925732A CN 116986995 A CN116986995 A CN 116986995A
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- SSJXIUAHEKJCMH-UHFFFAOYSA-N cyclohexane-1,2-diamine Chemical compound NC1CCCCC1N SSJXIUAHEKJCMH-UHFFFAOYSA-N 0.000 title claims abstract description 105
- BTGRAWJCKBQKAO-UHFFFAOYSA-N adiponitrile Chemical compound N#CCCCCC#N BTGRAWJCKBQKAO-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 51
- 238000000034 method Methods 0.000 title claims abstract description 48
- SYECJBOWSGTPLU-UHFFFAOYSA-N hexane-1,1-diamine Chemical compound CCCCCC(N)N SYECJBOWSGTPLU-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 230000015572 biosynthetic process Effects 0.000 title claims description 22
- 238000003786 synthesis reaction Methods 0.000 title claims description 22
- 238000007670 refining Methods 0.000 claims abstract description 86
- 239000007788 liquid Substances 0.000 claims abstract description 38
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 131
- VHRGRCVQAFMJIZ-UHFFFAOYSA-N cadaverine Chemical compound NCCCCCN VHRGRCVQAFMJIZ-UHFFFAOYSA-N 0.000 claims description 40
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 claims description 34
- 238000000926 separation method Methods 0.000 claims description 33
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 28
- 238000000746 purification Methods 0.000 claims description 27
- 238000010992 reflux Methods 0.000 claims description 25
- 239000012535 impurity Substances 0.000 claims description 24
- 230000002194 synthesizing effect Effects 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- XCIXKGXIYUWCLL-UHFFFAOYSA-N cyclopentanol Chemical compound OC1CCCC1 XCIXKGXIYUWCLL-UHFFFAOYSA-N 0.000 claims description 13
- 150000001298 alcohols Chemical class 0.000 claims description 6
- -1 alcohol compound Chemical class 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 230000000704 physical effect Effects 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 51
- 239000002994 raw material Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000009835 boiling Methods 0.000 description 4
- 229960003263 cyclopentamine Drugs 0.000 description 4
- 238000005235 decoking Methods 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- PFURGBBHAOXLIO-UHFFFAOYSA-N cyclohexane-1,2-diol Chemical compound OC1CCCCC1O PFURGBBHAOXLIO-UHFFFAOYSA-N 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- PQMCFTMVQORYJC-UHFFFAOYSA-N 2-aminocyclohexan-1-ol Chemical compound NC1CCCCC1O PQMCFTMVQORYJC-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 239000002246 antineoplastic agent Substances 0.000 description 1
- 229940041181 antineoplastic drug Drugs 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- ZWAJLVLEBYIOTI-UHFFFAOYSA-N cyclohexene oxide Chemical compound C1CCCC2OC21 ZWAJLVLEBYIOTI-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229960001756 oxaliplatin Drugs 0.000 description 1
- DWAFYCQODLXJNR-BNTLRKBRSA-L oxaliplatin Chemical compound O1C(=O)C(=O)O[Pt]11N[C@@H]2CCCC[C@H]2N1 DWAFYCQODLXJNR-BNTLRKBRSA-L 0.000 description 1
- KJOMYNHMBRNCNY-UHFFFAOYSA-N pentane-1,1-diamine Chemical compound CCCCC(N)N KJOMYNHMBRNCNY-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/82—Purification; Separation; Stabilisation; Use of additives
- C07C209/86—Separation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/14—Fractional distillation or use of a fractionation or rectification column
- B01D3/143—Fractional distillation or use of a fractionation or rectification column by two or more of a fractionation, separation or rectification step
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/14—Fractional distillation or use of a fractionation or rectification column
- B01D3/32—Other features of fractionating columns ; Constructional details of fractionating columns not provided for in groups B01D3/16 - B01D3/30
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/42—Regulation; Control
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a method for separating and purifying 1, 2-cyclohexanediamine from a product of hexanediamine by hydrogenation of adiponitrile, which comprises the steps of rectifying the product of hexanediamine by hydrogenation of adiponitrile in a light component removal tower, collecting tower bottom liquid, sending the tower bottom liquid to a refining tower for rectification again, and extracting 1, 2-cyclohexanediamine from the top of the refining tower; according to the method, the 1, 2-cyclohexanediamine is successfully separated and purified from the hexanediamine synthesized by adiponitrile with complex components and similar physical properties by limiting the theoretical plate number of the light component removal tower, the tower top operation pressure and the tower bottom operation temperature, and the theoretical plate number of the limited refining tower, the tower top operation pressure and the tower top operation temperature, and the product quality and the production efficiency of the 1, 2-cyclohexanediamine are effectively improved.
Description
Technical Field
The invention belongs to the field of separation and purification, and particularly relates to a method for separating and purifying 1, 2-cyclohexanediamine from a product of hexanediamine synthesized by hydrogenation of adiponitrile.
Background
1, 2-cyclohexanediamine is an important chemical raw material, has wide application in various fields, such as chelating agent in textile industry and water treatment, can be used as high-grade epoxy curing agent in the coating industry, and is an important raw material of the third-generation platinum anticancer drug oxaliplatin in the pharmaceutical field. The method for obtaining the 1, 2-cyclohexanediamine comprises the steps of taking 2-aminocyclohexanol as a raw material for synthesis, taking 1, 2-cyclohexanediol as a raw material for synthesis, and taking epoxycyclohexane as a raw material for synthesis. However, 1, 2-cyclohexanediamine still originates mainly from the product of the hydrogenation of adiponitrile to hexamethylenediamine.
At present, the production devices for synthesizing hexamethylenediamine by hydrogenation of adiponitrile are more and more, and the scale is also larger and larger, so that the yield of 1, 2-cyclohexanediamine is also more and more, although the 1, 2-cyclohexanediamine is a light component at the top of a first light component removal tower in the process for synthesizing hexamethylenediamine by adiponitrile, the content of 1, 2-cyclohexanediamine is higher, but the light component composition at the top of the first light component removal tower is still more and more mixed, the mixture containing polyamine is directly used in industry with lower value, and the high-purity 1, 2-cyclohexanediamine and hexamethylenediamine are important chemical raw materials. The product is reasonably developed, so that the main components in the product are recovered and purified to a high-purity product, and the economic benefit and the social benefit of the product can be greatly improved.
CN113248389a discloses a production system of 1, 2-cyclohexanediamine, comprising a solid-liquid separation device, a dehydration tower, a decoking tower and a refining tower, wherein the material inlet of the solid-liquid separation device is connected with a gas-liquid separation, catalyst filtration and dealcoholization mixture source discharged from a reactor, the solid-liquid separation device is used for feeding the dehydration tower through an overflow pipe, the bottom discharge port of the dehydration tower is used for feeding the decoking tower through a first pipeline, the top discharge port of the decoking tower is used for feeding the refining tower through a second pipeline, the top discharge port of the refining tower is connected with a reflux pipeline through a condenser, a reflux tank, a discharge pump and a first valve are sequentially arranged on the reflux pipeline, the downstream end of the reflux pipeline is connected with the reflux pipeline, a discharge pipe is connected between the discharge pump and the first valve, the discharge pipe is provided with a second valve, and the refining tower is used for extracting 1, 2-cyclohexanediamine product, but the invention does not obtain high-purity 1, 2-cyclohexanediamine, and the present production process of 1, 2-cyclohexanediamine is less in production and less in the process of separating 1-cyclohexanediamine.
Shen Xiaojie in the literature of DCH separation technology, only the first light ends of the column are separated from the first material of the hexamethylenediamine producer, which consists of 1, 2-cyclohexanediamine (DCH) 54%,1, 6-Hexamethylenediamine (HMD) 34%, o-methylaminocyclopentamine (AMCPA) 6% and H 2 O6%, it was concluded that column chromatography could separate the mixture but there were some problems and that the normal rectification method did not allow for an efficient separation of DCH.
Therefore, developing a method for separating and purifying 1, 2-cyclohexanediamine from the product of the hydrogenation synthesis of hexamethylenediamine from adiponitrile is an urgent technical problem in the field.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a method for separating and purifying 1, 2-cyclohexanediamine from a product of hexanediamine hydrogenation synthesis from adiponitrile, which adopts a light component removal tower and a refining tower to match and limit the theoretical plate number, the operating pressure and the operating temperature of the light component removal tower and the refining tower, adopts a rectifying tower with high theoretical plate number to operate under the condition of high vacuum, successfully realizes the separation and the purification of the 1, 2-cyclohexanediamine, can continuously and stably obtain the 1, 2-cyclohexanediamine product with higher purity, and effectively improves the product quality and the production efficiency of the 1, 2-cyclohexanediamine.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a process for the separation and purification of 1, 2-cyclohexanediamine from the product of the hydrogenation of adiponitrile to hexamethylenediamine, said process comprising the steps of:
(1) Rectifying a product of synthesizing hexamethylenediamine by hydrogenation of adiponitrile in a light component removal tower, and collecting tower bottom liquid;
(2) Rectifying the tower bottom liquid obtained in the step (1) in a refining tower, and extracting 1, 2-cyclohexanediamine from the tower top to finish the separation and purification of the 1, 2-cyclohexanediamine;
the theoretical plate number of the light component removal tower is more than or equal to 30 (such as 35, 40, 45 or 50, etc.), the tower top operation pressure is-0.099 to-0.06 MpaG (such as-0.06 MpaG, -0.07MpaG, -0.08MpaG or-0.09 MpaG, etc.), and the tower bottom operation temperature is 115-160 ℃ (such as 120 ℃, 125 ℃, 130 ℃, 135 ℃, 140 ℃, 150 ℃ or 155 ℃ and the like);
the theoretical plate number of the refining tower is more than or equal to 40 (such as 45, 50, 55 or 60), the tower top operation pressure is-0.099 to-0.07 MpaG (such as-0.09 MpaG, -0.08MpaG or-0.07 MpaG), and the tower top operation temperature is 90-150 ℃ (such as 95 ℃, 105 ℃, 120 ℃, 130 ℃, 140 ℃, 145 ℃ or the like).
Since the boiling points of all components in the product of synthesizing hexamethylenediamine by hydrogenation of adiponitrile are very close to each other (the molecular weight of 1, 5-pentanediamine is 102.2, the boiling point is 180 ℃, the molecular weights of 1, 2-cyclohexanediamine and o-methylcyclopentylamine are 114.2, the boiling points are 190 ℃ and 199 ℃, the molecular weight of 1, 6-hexamethylenediamine is 116.2, and the boiling point is 205 ℃), the conventional separation and purification method is difficult to obtain high-purity 1, 2-cyclohexanediamine; the method provided by the invention adopts a light component removal tower and a refining tower to match, limits the theoretical plate number, the operating pressure and the operating temperature of the light component removal tower and the refining tower with high theoretical plate number and the tower bottom liquid of the light component removal tower under the condition of high vacuum are utilized to rectify, successfully separate and purify to obtain 1, 2-cyclohexanediamine; meanwhile, the temperature of the tower bottom of the light component removal tower is 115-160 ℃, so that the bottom liquid of the tower containing heat-sensitive substances (1, 2-cyclohexanediamine and 1, 6-cyclohexanediamine) is not easy to carbonize and coke, and the quality of the purified 1, 2-cyclohexanediamine can be further ensured to be higher.
Preferably, the product of the hydrogenation synthesis of hexamethylenediamine from adiponitrile comprises water, 1, 5-pentanediamine, 1, 2-cyclohexanediamine, o-methylaminocyclopentamine and 1, 6-hexamethylenediamine.
Preferably, the mass percentage of water in the product of synthesizing hexamethylenediamine by hydrogenation of adiponitrile is 1-5%, such as 1.5%, 2%, 2.5%, 3%, 3.5%, 4% or 4.5%, etc.
Preferably, the mass percentage of the 1, 5-pentanediamine in the product of synthesizing hexamethylenediamine by hydrogenation of adiponitrile is 0.1-5%, such as 0.5%, 1%, 2%, 3% or 4% and the like.
Preferably, the mass percentage of 1, 2-cyclohexanediamine in the product of the hydrogenation synthesis of hexamethylenediamine from adiponitrile is 40-88%, such as 45%, 50%, 55%, 60%, 65% or 70%.
Preferably, the product of synthesizing hexamethylenediamine by hydrogenation of adiponitrile contains 0.1-5.0% by mass of o-methylamino cyclopentamine (AMCPA), for example 0.5%, 1%, 2%, 3% or 4% by mass.
Preferably, the mass percentage of 1, 6-hexamethylenediamine in the product of synthesizing hexamethylenediamine by hydrogenation of adiponitrile is 10-58%, such as 15%, 25%, 35%, 45% or 55%.
Preferably, the product of synthesizing hexamethylenediamine by hydrogenating adiponitrile also comprises an alcohol compound and/or 1, 4-butanediamine.
Preferably, the sum of the mass percentages of the alcohol compounds in the product of synthesizing hexamethylenediamine by hydrogenating adiponitrile is 0-5000 ppm and is not equal to 0, such as 500ppm, 1000ppm, 2000ppm, 3000ppm or 4000ppm, etc.
Preferably, the alcohol compound includes ethanol and cyclopentanol.
Preferably, the mass percent of 1, 4-butanediamine in the product of synthesizing hexamethylenediamine by hydrogenating adiponitrile is 0-5000 ppm and is not equal to 0, such as 500ppm, 1000ppm, 2000ppm, 3000ppm or 4000ppm, etc.
Preferably, in the step (1), the feed inlet of the product of synthesizing hexamethylenediamine by hydrogenating adiponitrile is positioned at the 5 th to 25 th (such as 10, 15 or 20 th, etc.) blocks from bottom to top of the light ends removal column, and the number of theoretical plates of the light ends removal column is specifically determined.
Preferably, the reflux ratio of the light ends column is 10 to 30, for example 15, 20 or 25, etc.
Preferably, in the step (2), the feed inlet of the tower bottom liquid is positioned at the 10 th to 35 th (e.g. 15, 20, 25 or 30 th, etc.) plate of the refining tower from bottom to top, and the number of theoretical plates of the refining tower is specifically required to be combined for determination.
Preferably, the reflux ratio of the purification column is 10 to 20, for example 12, 15 or 17.
Preferably, water, 1, 5-pentanediamine, optionally 1, 4-butanediamine, optionally cyclopentanol and optionally ethanol are withdrawn at the top of the light ends column after said rectification of step (1).
Preferably, the refining tower in the step (2) is sequentially provided with a refining section, a impurity removing section and a stripping section from top to bottom, and the 1, 2-cyclohexanediamine is extracted from the top of the refining section.
Preferably, the impurity removal section is located in the 2 nd to 7 th (e.g. 2, 5 or 7 th, etc.) theoretical plate of the refining tower from bottom to top.
Preferably, the impurity removal section is provided with a side line, and the o-methylamino cyclopentylamine is extracted from the side line.
The refining tower adopted by the method provided by the invention is provided with a side extraction, mainly the tower bottom liquid of the refining tower returns to the hexamethylenediamine rectifying device, so that AMCPA can be accumulated in the whole hexamethylenediamine refining system, the separation difficulty of 1, 2-cyclohexanediamine and 1, 6-hexamethylenediamine is increased, and the separation effect of 1, 2-cyclohexanediamine and 1, 6-hexamethylenediamine is improved by arranging the side extraction of AMCPA.
Preferably, the 1, 6-hexamethylenediamine is withdrawn from the bottoms of the stripping section.
As a preferred technical solution of the present invention, the method includes the steps of:
(1) Feeding and rectifying the product of synthesizing hexamethylenediamine by hydrogenating adiponitrile comprising water, 1, 5-pentanediamine, 1, 2-cyclohexanediamine, o-methylaminocyclopentamine, 1, 6-hexamethylenediamine, optionally alcohol compounds and 1, 4-butanediamine from 5 th to 25 th plates of a light component removal tower from bottom to top, wherein the theoretical plate number of the light component removal tower is more than or equal to 30, the tower top operating pressure is-0.099 to-0.06 MPaG, the tower bottom operating temperature is 115-160 ℃, the reflux ratio is 10-30, collecting tower bottom liquid at the tower bottom, and collecting water, 1, 5-pentanediamine, 1, 4-butanediamine and optionally alcohol compounds at the tower top;
(2) Rectifying tower bottom liquid obtained in the step (1) in a refining tower sequentially provided with a refining section, a impurity removing section and a stripping section from top to bottom, wherein the theoretical plate number of the refining tower is more than or equal to 40, the tower top operating pressure is-0.099 to-0.07 MPaG, the tower top operating temperature is 90-150 ℃, the reflux ratio is 10-20, the feeding position of the tower bottom liquid is the position of the theoretical plate number from bottom to top 10-35 plates, the impurity removing section is positioned at the position of the 2 nd-7 plates of the refining tower from bottom to top, the impurity removing section is provided with a side line extraction, the o-methylamino cyclopentylamine is extracted from the side line of the impurity removing section, the 1, 2-cyclohexanediamine is extracted from the tower top of the refining section, the 1, 6-cyclohexanediamine is extracted from the tower bottom of the stripping section, and the separation and purification of the 1, 2-cyclohexanediamine are completed.
The method for separating and purifying 1, 2-cyclohexanediamine is a continuous separation process.
In a second aspect, the present invention provides the use of a process as described in the first aspect for the isolation and purification of 1, 2-cyclohexanediamine.
In a third aspect, the invention provides a separation and purification device for separating and purifying 1, 2-cyclohexanediamine from a product of adiponitrile hydrogenation synthesis of hexamethylenediamine, which is characterized by comprising a light component removal tower and a refining tower.
The separation and purification device for separating and purifying 1, 2-cyclohexanediamine from the product of hexanediamine hydrogenation synthesis from adiponitrile comprises a light component removing tower and a refining tower, wherein the device can be used for separating and purifying 1, 2-cyclohexanediamine from the product of hexanediamine hydrogenation synthesis from adiponitrile, the product of hexanediamine synthesis directly flows into the light component removing tower for rectification, the liquid in the bottom of the collecting tower flows into the refining tower for rectification, pure 1, 2-cyclohexanediamine is extracted from the top of the refining tower, meanwhile, 1, 6-hexanediamine can be directly extracted from the bottom of the refining tower, and the device can be directly connected with the 1, 6-hexanediamine refining device.
The theoretical plate number of the light component removal tower is more than or equal to 30 (such as 35, 40, 45 or 50, etc.), the tower top operation pressure is-0.099 to-0.06 MpaG (such as-0.06 MpaG, -0.07MpaG, -0.08MpaG or-0.09 MpaG, etc.), and the tower bottom operation temperature is 115-160 ℃ (such as 125 ℃, 130 ℃, 135 ℃, 140 ℃, 145 ℃, 150 ℃ or 160 ℃ and the like);
the theoretical plate number of the refining tower is more than or equal to 40 (such as 45, 50, 55 or 60), the tower top operation pressure is-0.099 to-0.07 MpaG (such as-0.09 MpaG, -0.08MpaG or-0.07 MpaG), and the tower top operation temperature is 90-150 ℃ (such as 95 ℃, 105 ℃, 120 ℃, 130 ℃, 140 ℃, 145 ℃ or the like).
Compared with the prior art, the invention has the following beneficial effects:
the method for separating and purifying 1, 2-cyclohexanediamine from the product of hexanediamine hydrogenation synthesis from adiponitrile is a continuous separation process, and comprises the steps of continuously feeding the product of hexanediamine hydrogenation synthesis from adiponitrile into a light component removal tower, rectifying in the light component removal tower, collecting tower bottom liquid, rectifying the obtained tower bottom liquid in a refining tower, and extracting 1, 2-cyclohexanediamine from the tower top; according to the method, 1, 2-cyclohexanediamine is successfully separated and purified from adiponitrile synthesized hexamethylenediamine products with complex components and similar physical properties by limiting the theoretical plate number of a light component removal tower to be more than or equal to 30, the tower top operation pressure to be-0.099 to-0.06 MPaG, the tower bottom operation temperature to be 115-160 ℃ and the theoretical plate number of a refining tower to be more than or equal to 40, the tower top operation pressure to be-0.099 to-0.07 MPaG and the tower top operation temperature to be 90-150 ℃, and the yield and the purity are both higher, so that the product quality and the production efficiency of the 1, 2-cyclohexanediamine are effectively improved.
Drawings
FIG. 1 is a process flow diagram of the method provided in example 1 for separating and purifying 1, 2-cyclohexanediamine from the product of the hydrogenation of adiponitrile to hexamethylenediamine;
wherein, the light component removing tower is 1-and the refining tower is 2-.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
The source of the product of synthesizing hexamethylenediamine by hydrogenation of adiponitrile used in the invention can be specifically referred to as CN113248389A.
Example 1
A method for separating and purifying 1, 2-cyclohexanediamine from a product of hexanediamine hydrogenation synthesis from adiponitrile comprises the following steps:
(1) Continuously feeding 3.5% of water, 0.05% of ethanol, 0.1% of cyclopentanol, 0.05% of 1, 4-butanediamine, 2% of 1, 5-pentanediamine, 41% of 1, 2-cyclohexanediamine, 2.6% of o-methylamino cyclopentamine and 50.7% of 1, 6-hexanediamine into a light component removal tower 1 with the theoretical plate number of 50 for rectification, wherein the feeding position is positioned at the 5 th plate from bottom to top, the tower top operation pressure of the light component removal tower 1 is-0.09 MPa (G), the tower top operation temperature is 128 ℃, the tower top operation temperature is 50 ℃, the reflux ratio is 20, and light components (including water, ethanol, cyclopentanol, 1, 4-butanediamine and 1, 5-pentanediamine) are extracted from the tower top, and the tower bottom is obtained;
(2) Rectifying the tower bottom liquid obtained in the step (1) in a refining tower 2 again, wherein the theoretical plate number of the refining tower 2 is 50, the feeding position of the tower bottom liquid is the position of a 24 th piece from bottom to top of the refining tower, the tower top operating pressure is-0.096 MPa (G), the tower top operating temperature is 100 ℃, the tower bottom operating temperature is 115.8 ℃, the reflux ratio is 12, a refining section, a impurity removing section and a stripping section are sequentially arranged from top to bottom, the impurity removing section is provided with a side line, the side line is arranged at the position of a 5 th theoretical plate from bottom to top of the refining tower 2, 1, 2-cyclohexanediamine (the purity is 99.5%) is extracted from the tower top of the refining section, and 1, 6-cyclohexanediamine is extracted from the side line and pumped to a hexamethylenediamine rectifying system, so as to finish the separation and purification of the 1, 2-cyclohexanediamine.
Example 2
A process for the separation and purification of 1, 2-cyclohexanediamine from the product of the hydrogenation of adiponitrile to hexamethylenediamine, said process comprising the steps of:
(1) Continuously feeding the product (the mass composition is that water is 1%, ethanol is 0.05%, cyclopentanol is 0.1%, 1, 4-butanediamine is 0.05%, 1, 5-pentanediamine is 0.1%, 1, 2-cyclohexanediamine is 88%, o-methylamino cyclopentamine is 0.7% and 1, 6-hexanediamine is 10%) of hexanediamine synthesized by hydrogenation of adiponitrile into a light component removing tower with the theoretical plate number of 30 for rectification, wherein the feeding position is positioned at the 5 th plate from bottom to top, the tower top operation pressure of the light component removing tower is-0.08 MPa (G), the tower bottom operation temperature is 140 ℃, the tower top operation temperature is 46 ℃, the reflux ratio is 30, water, ethanol, cyclopentanol, 1, 4-butanediamine and 1, 5-pentanediamine are extracted from the tower top, and the tower bottom is obtained to obtain tower bottom liquid;
(2) Rectifying the tower bottom liquid obtained in the step (1) in a refining tower, wherein the theoretical plate number of the refining tower is 55, the feeding position of the tower bottom liquid is the 35 th plate of the refining tower from bottom to top, the tower top operating pressure is-0.07 MPa (G), the tower top operating temperature is 145 ℃, the tower bottom operating temperature is 157.5 ℃, the reflux ratio is 10, a refining section, a impurity removing section and a stripping section are sequentially arranged from top to bottom, the impurity removing section is provided with a side line, the side line is arranged at the 5 th theoretical plate of the refining tower from bottom to top, 1, 2-cyclohexanediamine (purity is 99.2%) is extracted from the tower top of the refining section, and 1, 6-cyclohexanediamine is extracted from the side line and pumped to a hexamethylenediamine rectifying system to finish the separation and purification of the 1, 2-cyclohexanediamine.
Example 3
A process for the separation and purification of 1, 2-cyclohexanediamine from the product of the hydrogenation of adiponitrile to hexamethylenediamine, said process comprising the steps of:
(1) Continuously feeding 1% of water, 0.07% of ethanol, 0.08% of 1, 4-butanediamine, 0.55% of 1, 5-pentanediamine, 40% of 1, 2-cyclohexanediamine, 0.3% of o-methylamino cyclopentanamine and 58% of 1, 6-hexanediamine into a light component removing tower with a theoretical plate number of 50 for rectification, wherein the feeding position is at the position of 25 th plate from bottom to top, the tower top operating pressure is-0.09 MPa (G), the tower bottom operating temperature is 130.8 ℃, the tower top operating temperature is 50 ℃, the reflux ratio is 30, and the tower top is provided with water, ethanol, cyclopentanol and 1, 5-pentanediamine;
(2) Rectifying the tower bottom liquid obtained in the step (1) in a refining tower, wherein the theoretical plate number of the refining tower is 40, the feeding position is at the 10 th plate from bottom to top, the tower top operating pressure is-0.098 MPa (G), the tower top operating temperature is 90 ℃, the tower bottom operating temperature is 108 ℃, the reflux ratio is 20, a refining section, a impurity removing section and a stripping section are sequentially arranged from top to bottom, the impurity removing section is provided with a side line, the side line is arranged at the 5 th theoretical plate from bottom to top of the refining tower, 1, 2-cyclohexanediamine (purity is 99.5%) is extracted from the tower top of the refining section, o-methylaminocyclopentanamine is extracted from the side line, and the 1, 6-cyclohexanediamine is extracted from the tower bottom liquid and pumped to a hexamethylenediamine rectifying system, so that the separation and purification of the 1, 2-cyclohexanediamine are completed.
Example 4
A process for the separation and purification of 1, 2-cyclohexanediamine from the product of the hydrogenation of adiponitrile to hexamethylenediamine, said process comprising the steps of:
(1) Continuously feeding the product (the mass composition is that water is 5%, ethanol is 0.3%, cyclopentanol is 0.2%,1, 4-butanediamine is 0.5%, 1, 5-pentanediamine is 5%, 1, 2-cyclohexanediamine is 50%, o-methylamino cyclopentamine is 5% and 1, 6-hexanediamine is 34%) of hexanediamine synthesized by hydrogenation of adiponitrile into a light component removing tower with the theoretical plate number of 55 for rectification, wherein the feeding position is at the position of 25 th plate from bottom to top, the tower top operating pressure is-0.06 MPa (G), the tower bottom operating temperature is 157.5 ℃, the tower top operating temperature is 58 ℃, the reflux ratio is 10, and water, ethanol, cyclopentanol, 1, 4-butanediamine and 1, 5-pentanediamine are extracted from the tower top, and the tower bottom is obtained as tower bottom liquid;
(2) Rectifying the tower bottom liquid obtained in the step (1) in a refining tower, wherein the theoretical plate number of the refining tower is 40, the feeding position is at the 22 th plate from bottom to top, the tower top operating pressure is-0.088 MPa (G), the tower top operating temperature is 124 ℃, the tower bottom operating temperature is 137 ℃, the reflux ratio is 15, a refining section, a impurity removing section and a stripping section are sequentially arranged from top to bottom, the bottom of the impurity removing section is provided with a side line, the side line is arranged at the 7 th theoretical plate from bottom to top of the refining tower, 1, 2-cyclohexanediamine (purity is 99.2%) is extracted from the tower top of the refining section, and the o-methylaminocyclopentanamine is extracted from the side line, and the tower bottom liquid is obtained from the tower bottom and pumped to a hexamethylenediamine rectifying system to finish the separation and purification of the 1, 2-cyclohexanediamine.
Example 5
A process for separating and purifying 1, 2-cyclohexanediamine from the product of the hydrogenation synthesis of adiponitrile, which differs from example 1 only in that the operating pressure at the top of the light ends removal column is-0.099 MPaG, the operating temperature at the bottom of the column is 115 ℃, the operating pressure at the top of the refining column is-0.099 MPaG, the operating temperature at the top of the column is 90 ℃, and other parameters and steps are the same as in example 1.
Example 6
A process for the separation and purification of 1, 2-cyclohexanediamine from the product of the hydrogenation of adiponitrile to hexamethylenediamine, said process comprising the steps of:
(1) Continuously feeding 3.0% of water, 0.06% of ethanol, 0.1% of cyclopentanol, 2% of 1, 5-pentanediamine, 52% of 1, 2-cyclohexanediamine, 2.1% of o-methylaminocyclopentamine and 40.74% of 1, 6-hexanediamine into a light component removing tower with the theoretical plate number of 40 for rectification, wherein the feeding position is at the 6 th plate from bottom to top, the tower top operating pressure is-0.087 MPa (G), the tower bottom operating temperature is 134 ℃, the tower top operating temperature is 50 ℃, the reflux ratio is 15, the tower top water, ethanol, 1, 5-cyclopentanol and pentanediamine are extracted, and the tower bottom liquid enters a refining tower;
(2) Rectifying the tower bottom liquid obtained in the step (1) in a refining tower, wherein the theoretical plate number of the refining tower is 50, the feeding position is at a 26 th plate from bottom to top, the tower top operating pressure is-0.095 MPa (G), the tower top operating temperature is 104.3 ℃, the tower bottom operating temperature is 118.6 ℃, the reflux ratio is 15, a refining section, a impurity removing section and a stripping section are sequentially arranged from top to bottom, the bottom of the impurity removing section is provided with a side line, the side line is arranged at a 2 nd theoretical plate from bottom to top of the refining tower, 1, 2-cyclohexanediamine (the purity is 99.6%) is extracted from the tower top of the refining section, and the tower bottom liquid 1, 6-cyclohexanediamine is obtained from the tower bottom and pumped to a hexamethylenediamine rectifying system to finish the separation and purification of the 1, 2-cyclohexanediamine.
Example 7
A method for separating and purifying 1, 2-cyclohexanediamine from a product of hexanediamine hydrogenation synthesis from adiponitrile is different from example 1 only in that the feeding position of the tower bottom liquid in the step (2) is located on the 8 th plate from bottom to top of the refining tower, and other parameters and steps are the same as those in example 1.
Example 8
A process for separating and purifying 1, 2-cyclohexanediamine from the product of the hydrogenation of adiponitrile to hexamethylenediamine, which differs from example 1 only in that the reflux ratio of the refining column is 6, and the other parameters and steps are the same as in example 1.
Comparative example 1
A process for separating and purifying 1, 2-cyclohexanediamine from the product of the hydrogenation of adiponitrile to hexamethylenediamine, which differs from example 1 only in that the theoretical plate number of the purifying column is 25, and other parameters and steps are the same as in example 1.
Comparative example 2
A process for separating and purifying 1, 2-cyclohexanediamine from the product of the hydrogenation synthesis of adiponitrile, which differs from example 1 only in that the operating pressure at the top of the refining column is-0.06 MPaG, the operating temperature at the top of the column is 159 ℃, the operating temperature at the bottom of the column is 168 ℃, and other parameters and steps are the same as in example 1.
Performance test:
(1) Yield of 1, 2-cyclohexanediamine: 1, 2-cyclohexanediamine yield = 1, 2-cyclohexanediamine amount x 100% in the product/raw material that meets the requirements;
(2) Purity of 1, 2-cyclohexanediamine: detection was performed by gas chromatography.
The samples provided in examples 1 to 8 and comparative examples 1 to 2 were tested according to the test methods described above, and the test results are shown in table 1:
TABLE 1
From the data in table 1, it can be seen that:
the purity of 1, 2-cyclohexanediamine in the products obtained in examples 1 to 6 is 99.2 to 99.6%, and the yield of 1, 2-cyclohexanediamine is 90.9 to 95.5%;
comparing the data of example 1 and comparative example 1, it was found that too low a theoretical plate count of the refining column resulted in a decrease in both the purity and yield of 1, 2-cyclohexanediamine in the final product;
comparing the data of example 1 and comparative example 2, it was found that the overhead operating pressure and operating temperature of the refining column were not within the limits of the present invention, and that the purity and yield of 1, 2-cyclohexanediamine in the final product were also decreased.
Further, it was found by comparing the data of example 1 with the data of examples 7 to 8 that the feed position of the column bottoms and the reflux ratio of the purification column also affect the purity and yield of the finally obtained 1, 2-cyclohexanediamine.
The applicant states that the present invention, by way of the above examples, illustrates a process for the separation and purification of 1, 2-cyclohexanediamine from the product of the hydrogenation of adiponitrile to hexamethylenediamine, but the invention is not limited to, i.e. it does not necessarily depend on, the above process steps. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of selected raw materials, addition of auxiliary components, selection of specific modes, etc. fall within the scope of the present invention and the scope of disclosure.
Claims (10)
1. A process for the separation and purification of 1, 2-cyclohexanediamine from the product of the hydrogenation of adiponitrile to hexamethylenediamine, comprising the steps of:
(1) Rectifying a product of synthesizing hexamethylenediamine by hydrogenation of adiponitrile in a light component removal tower, and collecting tower bottom liquid;
(2) Rectifying the tower bottom liquid obtained in the step (1) in a refining tower, and extracting 1, 2-cyclohexanediamine from the tower top to finish the separation and purification of the 1, 2-cyclohexanediamine;
the theoretical plate number of the light component removal tower is more than or equal to 30, the tower top operation pressure is-0.099 to-0.06 MPaG, and the tower bottom operation temperature is 115-160 ℃;
the theoretical plate number of the refining tower is more than or equal to 40, the tower top operation pressure is-0.099 to-0.07 MPaG, and the tower top operation temperature is 90-150 ℃.
2. The process of claim 1, wherein the product of the hydrogenation of adiponitrile to hexamethylenediamine comprises water, 1, 5-pentanediamine, 1, 2-cyclohexanediamine, o-methylaminocyclopentamine, and 1, 6-hexamethylenediamine;
preferably, the mass percentage of water in the product of synthesizing hexamethylenediamine by hydrogenation of adiponitrile is 1-5%;
preferably, the mass percentage of the 1, 5-pentanediamine in the product of synthesizing hexamethylenediamine by hydrogenation of adiponitrile is 0.1-5%;
preferably, the mass percentage of 1, 2-cyclohexanediamine in the product of the hexanediamine hydrogenation synthesis of adiponitrile is 40-88%;
preferably, the mass percentage of the o-methylamino cyclopentylamine in the product of synthesizing hexamethylenediamine by hydrogenation of adiponitrile is 0.1-5%;
preferably, the mass percentage of 1, 6-hexamethylenediamine in the product of synthesizing hexamethylenediamine by hydrogenation of adiponitrile is 10-58%.
3. The method according to claim 1 or 2, wherein the product of the hydrogenation synthesis of hexamethylenediamine from adiponitrile further comprises an alcohol compound and/or 1, 4-butanediamine;
preferably, the sum of the mass percentages of the alcohol compounds in the product of synthesizing hexamethylenediamine by hydrogenation of adiponitrile is 0-5000 ppm and is not equal to 0;
preferably, the alcohol compound comprises ethanol and/or cyclopentanol;
preferably, the mass percentage of 1, 4-butanediamine in the product of synthesizing hexamethylenediamine by hydrogenation of adiponitrile is 0-5000 ppm and is not equal to 0.
4. A process according to any one of claims 1 to 3, wherein in step (1), the feed inlet for the product of the hydrogenation of adiponitrile to hexamethylenediamine is located at the 5 th to 25 th plate of the lightness-removing column from bottom to top;
preferably, the reflux ratio of the light component removal tower is 10-30.
5. The method according to any one of claims 1 to 4, wherein in step (2), the inlet for the bottoms liquid is located at the 10 th to 35 th plate of the refining tower from bottom to top;
preferably, the reflux ratio of the purification column is 10 to 20.
6. The process according to any one of claims 1 to 5, wherein water, 1, 5-pentanediamine, 1, 4-butanediamine, optionally cyclopentanol and optionally ethanol are withdrawn at the top of the light ends column after the rectification of step (1).
7. The method according to any one of claims 1 to 6, wherein the refining tower in step (2) is provided with a refining section, a impurity removing section and a stripping section in order from top to bottom, and the 1, 2-cyclohexanediamine is extracted from the top of the refining section;
preferably, the impurity removing section is positioned at the 2 nd to 7 th plates of the refining tower from bottom to top;
preferably, the impurity removal section is provided with a side line from which the o-methylamino cyclopentylamine is extracted;
preferably, the 1, 6-hexamethylenediamine is withdrawn from the bottoms of the stripping section.
8. The method according to any one of claims 1 to 7, characterized in that it comprises the steps of:
(1) Rectifying the product of synthesizing hexamethylenediamine by hydrogenating adiponitrile, which comprises water, 1, 5-pentanediamine, 1, 2-cyclohexanediamine, o-methylaminocyclopentamine, 1, 6-hexamethylenediamine, optionally alcohol compounds and 1, 4-butanediamine, from 5 th to 25 th plates of a light component removal tower from bottom to top, wherein the theoretical plate number of the light component removal tower is more than or equal to 30, the tower top operating pressure is-0.099 to-0.06 MPaG, the tower bottom operating temperature is 115-160 ℃ and the reflux ratio is 10-30, collecting tower bottom liquid at the tower bottom of the light component removal tower, and collecting water, 1, 5-pentanediamine, 1, 4-butanediamine and optionally alcohol compounds at the tower top;
(2) Rectifying the tower bottom liquid obtained in the step (1) in a refining tower which is sequentially provided with a refining section, a impurity removing section and a stripping section from top to bottom, wherein the theoretical plate number of the refining tower is more than or equal to 40, the tower top operating pressure is-0.099 to-0.07 MPaG, the tower top operating temperature is 90-150 ℃, the reflux ratio is 10-20, the feeding position of the tower bottom liquid is positioned at the 10-35 th plate of the refining tower from bottom to top, the impurity removing section is positioned at the 2-7 th plate of the refining tower from bottom to top, the impurity removing section is provided with a side line, the o-methylaminocyclopentanamine is extracted from the side line of the impurity removing section, the 1, 2-cyclohexanediamine is extracted from the tower top of the refining section, the 1, 6-cyclohexanediamine is extracted from the tower bottom of the stripping section, and the separation and purification of the 1, 2-cyclohexanediamine are completed.
9. Use of a method according to any one of claims 1 to 8 for the separation and purification of 1, 2-cyclohexanediamine.
10. A separation and purification device for separating and purifying 1, 2-cyclohexanediamine from a product of hexanediamine hydrogenation synthesis from adiponitrile, which is characterized by comprising a light component removal tower and a refining tower;
the theoretical plate number of the light component removal tower is more than or equal to 30, the tower top operation pressure is-0.099 to-0.06 MPaG, and the tower bottom operation temperature is 115-160 ℃;
the theoretical plate number of the refining tower is more than or equal to 40, the tower top operation pressure is-0.099 to-0.07 MPaG, and the tower top operation temperature is 90-150 ℃.
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| CN202310925732.0A CN116986995A (en) | 2023-07-26 | 2023-07-26 | Method for separating and purifying 1, 2-cyclohexanediamine from product of hexanediamine hydrogenation synthesis from adiponitrile |
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| CN202310925732.0A CN116986995A (en) | 2023-07-26 | 2023-07-26 | Method for separating and purifying 1, 2-cyclohexanediamine from product of hexanediamine hydrogenation synthesis from adiponitrile |
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