Vinylamine pilot scale production system

Abstract

The invention discloses a vinylamine pilot scale production system, which belongs to the technical field of vinylamine production, and comprises a feeding unit, a reactor unit, a rectification unit, a storage area, an auxiliary function area and a public project which are respectively and independently assembled into a skid-mounted module and are arranged in multiple layers. The problems that a traditional industrial production device for vinylamine is long in production process flow, high in reaction pressure and complex in equipment are solved, and the industrial production device is mainly applied to pilot test of vinylamine.

Description

Technical Field

[0001] The invention relates to the technical field of oil production, in particular to an ethyleneamine pilot production system. Background Art

[0002] Ethyleneamine (also known as ethyleneamine) is a series of products including ethylenediamine (EDA) and its homologous polyethylene polyamines. It is an important organic chemical raw material with a wide range of uses. In recent years, the consumption of ethyleneamine in my country has grown rapidly, and is mainly used in epoxy resin curing agents, pesticides, medicines, low molecular weight polyamide resins and other fields.

[0003] The traditional ethyleneamine industrial production equipment has a long production process, high reaction pressure, and complex equipment. When conducting industrial pilot and catalyst screening and performance improvement, if the existing process is copied, there are often many disadvantages, such as the inability to meet the initial regeneration of the catalyst, rapid switching of catalyst categories, online monitoring of product and raw material quality, quantitative analysis of reactor yield, analysis of the impact of process impurities, and the continuity and stability of the pilot equipment are difficult to meet the requirements of long-term operation. Therefore, it is necessary to improve the design of the ethyleneamine industrial experimental equipment. Summary of the invention

[0004] The object of the present invention is to provide an ethyleneamine pilot production system to solve the existing technology proposed in the above background technology, while shortening the test period and material consumption.

[0005] The raw material liquid ammonia (NH3) and monoethanolamine (MEA) undergo an amination reaction under pressure and temperature in the presence and action of hydrogen and a catalyst to produce a series of ethyleneamine products.

[0006] The main reactions in this process are as follows:

[0007] Main reaction:

[0008] Ammonia (NH3) + monoethanolamine (MEA) → ethylenediamine (EDA) + water (H2O)

[0009] Main side effects:

[0010] Monoethanolamine (MEA) + ethylenediamine (EDA) → diethylenetriamine (DETA) + water (H2O)

[0011] Monoethanolamine (MEA) + monoethanolamine (MEA) → aminoethylethylenediamine (AEEA) + water (H2O)

[0012] Ethylenediamine (EDA) + Ethylenediamine (EDA) → Piperazine (PIP) + Ammonia (2NH3)

[0013] Ethylenediamine (EDA) + monoethanolamine (MEA) → diethylenetriamine (DETA) + water (H2O)

[0014] Ethylenediamine (EDA) + piperazine (PIP) → aminoethylpiperazine (AEP) + ammonia (NH3)

[0015] Aminoethylethylenediamine (AEEA) + monoethanolamine (MEA) → mixed amine (SMA) + water (H2O)

[0016] Aminoethylethylenediamine (AEEA) + ethylenediamine (EDA) → mixed amine (SMA) + ammonia (NH3)

[0017] Diethylenetriamine (DETA) + monoethanolamine (MEA) → mixed amine (SMA) + water (H2O)

[0018] Diethylenetriamine (DETA) + ethylenediamine (EDA) → mixed amine (SMA) + ammonia (NH3)

[0019] Monoethanolamine (MEA) + piperazine (PIP) → aminoethylpiperazine (AEP) + water (H2O)

[0020] Hydroxyethylpiperazine (HEP) + ammonia (NH3) → aminoethylpiperazine (AEP)

[0021] These reactions are a series of chain reactions. MEA, ammonia, and primary ethyleneamines (such as EDA, DETA, etc.) will continue to react slightly under the action of hydrogenation and catalysts in the reactor to further generate a series of long-chain and branched organic amines such as triethylenetetramine, tetraethylenepentamine, C4+ heavy amines, and polyamines (HPA).

[0022] In the distillation unit, through reasonable process design, the recovery of unreacted hydrogen, liquid ammonia, MEA and other raw materials, impurity removal, ethyleneamine product dehydration, separation and distillation purification of various products are completed. An ethyleneamine pilot production system is characterized by comprising a feed unit, a reactor unit, a distillation unit, a storage area, an auxiliary functional area, and a utility project, which are separately assembled into skid-mounted modules and arranged in multiple layers.

[0023] Preferably, the distillation tower and tail gas purification tower skids are separate components.

[0024] Preferably, the reaction unit is composed of a main reactor, a secondary reactor, an auxiliary reactor, a first functional reactor and a second functional reactor which are coupled to each other.

[0025] Preferably, the feeding unit module is a mixed feed of MEA / NH3 / H2 or a separate feed, the reactor module is a reactor, and the components inside the reactor are: MEA 20-60%, NH3 40-80%, H2 0-5% by weight wt%, and the distillation tower module is a distillation tower to recover ammonia, Vd / VR=4:1-10:1, the operating pressure is 1.6-2.6Mpa, the working temperature is 60-240°C, and RR=2-4.

[0026] Preferably, the second-stage reactor is used as a supplementary extension of the first-stage reactor to improve product quality. The volume of the second-stage reactor is 30% to 150% of the main reactor, the operating pressure is 10 to 30 MPa, and the working temperature is 50 to 300°C.

[0027] Preferably, the auxiliary reactor is used to test different catalyst systems and feed combinations, and can produce by-product high and low component products. It is 40% to 80% of the volume of the main reactor, with an operating pressure of 10 to 40 MPa and an operating temperature of 80 to 260°C.

[0028] Preferably, the raw materials of the main reactor, the secondary reactor, the auxiliary reactor, the first functional reactor and the second functional reactor provide compounds for hydrogenation reaction under the conditions of hydroamination reaction, wherein the raw materials include but are not limited to monoethanolamine and ammonia, hydrogen, hydrogen is a catalyst protection gas, and is added to the main reactor, the secondary reactor, the auxiliary reactor, the first functional reactor and the second functional reactor respectively before the reaction so that the reactor is in a hydrogen atmosphere, and the amount of hydrogen is 0.50-5.0% of the weight of the monomer. The monoethanolamine feed ratio accounts for 20-80% of the total feed composition, and the ammonia feed ratio accounts for 20-80% of the total feed composition.

[0029] Preferably, the first functional reactor and the second functional reactor are used to produce functional ethyleneamine products, the first functional reactor and the second functional reactor are connected in parallel or in series, and the feed composition includes functional monomers in addition to monoethanolamine, ammonia and hydrogen, namely, one or a combination of more than two of ethylenediamine, aminoethylethanolamine, diethanolamine, hydroxyethylpiperazine, diethylenetriamine and ethylene oxide, and the feed ratio of the functional monomers accounts for 20-100% of the total feed composition. Among the various functional monomer feeds, ethylenediamine accounts for 0-100% of the total feed composition, aminoethylethanolamine accounts for 0-50% of the total feed composition, diethanolamine accounts for 0-15% of the total feed composition, hydroxyethylpiperazine accounts for 0-20% of the total feed composition, diethylenetriamine accounts for 0-60% of the total feed composition, and ethylene oxide accounts for 0-30% of the total feed composition.

[0030] Preferably, different ammonia recovery systems are designed according to the test scale and the impact of impurity evaluation, that is, the distillation unit is a single flash process, a flash and stripping combined process, and an ammonia recovery and refining combined process.

[0031] Compared with the prior art, the technical effects and advantages of the present invention are:

[0032] The pilot plant prepared by the present invention has the following advantages:

[0033] The ethyleneamine product of the present invention is a multi-component mixture consisting of one or more of ethylenediamine, piperazine, diethylenetriamine, polyethylenepolyamine, hydroxypolyamine, aminopolyamine and the like.

[0034] The pilot plant prepared by the present invention uses a skid design, which can flexibly match different units and working conditions with different qualities of raw materials / process media, and can be expanded, which can greatly save the test cost;

[0035] The modular arrangement prepared by the present invention has flexible safety spacing and high overall safety;

[0036] The method has simple process, is easy to control, has a wide adjustable range of raw materials and products, has good quality stability, and has a wide experimental range.

[0037] The present invention is applicable to rapid evaluation and industrial research tests of multiple categories of catalysts;

[0038] The influence of impurities in the raw materials can be adjusted within the range of 80% to 100%. This reduces production costs and is suitable for comprehensive promotion and application. BRIEF DESCRIPTION OF THE DRAWINGS

[0039] Figure 1 is a process flow chart of ethyleneamine of the present invention;

[0040] Figure 2 The combined flow chart of the pilot plant of the ethyleneamine process of the present invention is as follows;

[0041] Figure 3 The reactor structure design of the pilot plant of the ethyleneamine process of the present invention Figure 1 ;

[0042] Figure 4 The reactor structure design of the pilot plant of the ethyleneamine process of the present invention Figure 2 ;

[0043] Figure 5 The structure design of the refining unit of the ethyleneamine process pilot plant of the present invention Figure 1 ;

[0044] Figure 6 The structure design of the refining unit of the ethyleneamine process pilot plant of the present invention Figure 2 ;

[0045] Figure 7 The structure design of the refining unit of the ethyleneamine process pilot plant of the present invention Figure 3 . DETAILED DESCRIPTION

[0046] The following will be combined with the accompanying drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Figure 1 It belongs to the protection scope of the present invention.

[0047] In one embodiment, the module design and structure

[0048] 3~2 Refining unit design D

[0049] The design of the refining unit can be determined according to the pilot scale and requirements and site conditions, and can be adopted in the following ways:

[0050] See also Figure 1 Taking the minimization design case as an example, the typical pilot plant module consists of a feed unit A, a reactor unit B, a distillation unit D, and a utility F, as follows:

[0051]

[0052] According to the scale of the pilot test, on this basis, the functional units will be divided, and modular and convenient splicing and combination design will be carried out to appropriately expand and strengthen the functionality of each unit to meet the needs of different pilot plants. For relevant specific implementation cases, please refer to the embodiments.

[0053] (1) Module design and structure

[0054] The structured unit design and skid-mounted components are adopted. The raw material area A, reaction area B, main distribution unit C, compressor unit X, distillation area D, storage area E, utility F and auxiliary function area G are separately assembled into skid-mounted modules. The main skid blocks maintain the size of length * width * height of about (2~5)m*(2~5)m*(2~10)m, and are arranged in multiple layers. Feed unit module A, MEA / NH3 / H2 mixed feed or separate feed, reactor module B is a reactor, the internal components of the reactor are: MEA 20~60%, NH3 40~80%, H2 0~5% by weight wt%, distillation tower module D, a distillation tower to recover ammonia, Vd / VR=4:1~10:1, operating pressure 1.6~2.6Mpa, working temperature 60~240℃, RR=2~4.

[0055] The distillation tower D and the tail gas purification tower G skids are separate components to reduce the size of the structural frame of the main device area and maintain a safe distance, simplifying the installation process. The reaction unit B is divided into a main reactor 1, a secondary reactor 2, an auxiliary reactor 3, a first functional reactor 4 and a second functional reactor 5, which are coupled to each other.

[0056] The size of each unit is optimized based on site conditions and equipment results.

[0057] In addition to the above modules, the video monitoring station H and DCS operation station I, fire protection system J, gas alarm system K, and power distribution system L adopt independent module design.

[0058] (2) Layout

[0059] The skid-mounted blocks are assembled flexibly, and the main units can be matched and selected to meet functional requirements.

[0060] Each skid-mounted block is laid out separately and adopts a ring structure to meet safety requirements.

[0061] (3) Unit design, see Figure 2

[0062] 3~1 Reactor Unit Design B

[0063] The reaction unit B mentioned is divided into a main reactor 1, a secondary reactor 2, an auxiliary reactor 3, a first functional reactor 4 and a second functional reactor 5 which are coupled to each other. The secondary reactor 2 serves as a supplementary extension of the main reactor 1 to improve product quality. The secondary reactor 2 is 30% to 150% of the volume of the main reactor 1, with an operating pressure of 10 to 30 MPa and a working temperature of 50 to 300°C.

[0064] The reaction raw materials provide compounds for hydrogenation reaction under the conditions of hydroamination reaction, wherein the raw materials include but are not limited to monoethanolamine and ammonia, hydrogen, hydrogen is a catalyst protection gas, and is added to the main reactor 1, the secondary reactor 2, the auxiliary reactor 3, the first functional reactor 4 and the second functional reactor 5 respectively before the reaction, so that the reactor is in a hydrogen atmosphere, and the amount of hydrogen is 0.50-5.0% by weight of the monomer. The monoethanolamine feed ratio accounts for 20-80% of the total feed composition, and the ammonia feed ratio accounts for 20-80% of the total feed composition.

[0065] The first functional reactor 4 and the second functional reactor 5 are used to produce functional ethyleneamine products. The first functional reactor 4 and the second functional reactor 5 are connected in parallel or in series. The feed composition includes functional monomers in addition to monoethanolamine, ammonia and hydrogen, namely, one or a combination of more than two of ethylenediamine, aminoethylethanolamine, diethanolamine, hydroxyethylpiperazine, diethylenetriamine and ethylene oxide. The feed ratio of the functional monomers accounts for 20-100% of the total feed composition. Among the various functional monomer feeds, ethylenediamine accounts for 0-100% of the total feed composition, aminoethylethanolamine accounts for 0-50% of the total feed composition, diethanolamine accounts for 0-15% of the total feed composition, hydroxyethylpiperazine accounts for 0-20% of the total feed composition, diethylenetriamine accounts for 0-60% of the total feed composition, and ethylene oxide accounts for 0-30% of the total feed composition.

[0066] Preferably, different ammonia recovery systems are designed according to the test scale and the impact of impurity evaluation, that is, the distillation unit D is a single flash process D-1, a flash and stripping combined process D-2 and an ammonia recovery and refining combined process D-3.

[0067] See also Figure 3 , main reactor 1 and secondary reactor 2,: the main reactor 1 is determined according to the dosage of the pilot catalyst, with a typical operating pressure of 10-30Mpa and an operating temperature of 110-260°C.

[0068] The secondary reactor 2 is a supplement and extension of the main reactor 1. The reaction conditions and product differences under different reaction conditions are tested. The secondary reactor 2 is 30% to 150% of the volume of the main reactor 1. According to the reaction characteristics and the type, state, feed composition and ratio of the loaded catalyst, the typical operating pressure is 10 to 30 MPa and the operating temperature is 50 to 300°C.

[0069] Auxiliary reactor 3: According to the test requirements, if it is necessary to evaluate the effects of different types of catalysts and raw materials, reaction conditions, etc., an auxiliary reactor can be added.

[0070] Mainly for by-product high and low component products, designed to be 40% to 80% of the volume of the main reactor 1. According to the reaction characteristics and catalyst state, feed composition and ratio, adjust the operating parameters, the typical operating pressure is 10 to 40Mpa, and the working temperature is 80 to 260℃.

[0071] The first functional reactor 4 and the second functional reactor 5: additional functional reactors can be set up according to test requirements, such as when it is necessary to increase the production of products with special structures or to evaluate the effects of different types of catalysts and raw materials.

[0072] Mainly for the production of directional products with special structures, it accounts for 20% to 60% of the volume of the main reactor. According to the characteristics of the catalyst, the typical operating pressure is 10 to 28 MPa and the working temperature is 90 to 260°C.

[0073] The first functional reactor 4 and the second functional reactor 5 are generally arranged in parallel and can be operated independently. Depending on the functional reaction conditions, the design of the reactor, and the type of catalyst, a series structure can also be adopted.

[0074] Each reactor should preferably adopt an independent feeding system for the main reactor 1, the secondary reactor 2, the auxiliary reactor 3, the first functional reactor 4 and the second functional reactor 5. According to the test requirements, a mixed feeding method can also be adopted to simplify the design and reduce the number of equipment.

[0075] The reaction raw materials suitable for the present invention are compounds that can provide hydrogenation reaction under the conditions of hydroamination reaction. Among them, typical raw materials include but are not limited to monoethanolamine and ammonia.

[0076] Hydrogen is used as a catalyst activation gas and is added before the reaction to place the reactor in a hydrogen atmosphere. The amount of hydrogen used is 0.50-5.0% by weight of the monomers.

[0077] Functional monomers include ethylenediamine, aminoethylethanolamine, diethanolamine, hydroxyethylpiperazine, diethylenetriamine, ethylene oxide, etc. Functional monomers are used to adjust the production of specific reaction products to achieve a reasonable ratio of the final product. The working conditions of the functional reactor are usually different from those of the main and auxiliary reactors, such as temperature, pressure, composition, and loading catalyst. Through differentiated settings, the production of certain specific products can be met.

[0078] According to the reaction conditions of the first-stage product, the distillate of the main reactor 1 (including the distillate of the main reactor 1, the distillate of the auxiliary reactor 3, the distillate of the first functional reactor 4 and the distillate of the second functional reactor 5) can be controlled to enter the secondary reactor 2 in part or in whole to continue to participate in the reaction. Before entering the secondary reactor 2, functional monomers, liquid ammonia and hydrogen can be added to adjust the raw material composition.

[0079] The ethyleneamine product of the present invention is a multi-component mixture of one or more of ethylenediamine, piperazine, diethylenetriamine, polyethylenepolyamine, hydroxypolyamine, aminopolyamine, etc. Each raw material and monomer of the present invention adopts a separate storage and feeding unit A, a separate metering and conveying module, and is matched with a reactor unit B and a distillation unit D.

[0080] 3~2 Refining unit design D

[0081] The design of the refining unit is determined according to the pilot scale and requirements and site conditions, and adopts the following methods:

[0082] See also Figure 4, a single flash process, i.e. D-1, uses a single tower to recover gas and liquid ammonia from the reaction effluent. The combined tower responsible for the separation of the main reaction products is a two-stage structure, the lower part of the tower is the flash zone, and the upper area of ​​the tower is the distillation zone. The total volume of the tower accounts for 300-800% of the total reactor volume, the operating pressure is 0.2-3.0Mpa, and the working temperature is 60-260℃.

[0083] See also Figure 5 , flash and stripping combined process, namely D-2, uses two towers in series to recover gas and purify liquid ammonia from the reaction effluent. The primary tower responsible for the separation of the main reaction product occupies 200-800% of the total reactor volume, with an operating pressure of 1.0-3.0Mpa and an operating temperature of 60-260℃. The secondary tower occupies 150-400% of the total reactor volume, with an operating pressure of 0-1.0Mpa and an operating temperature of 0-200℃.

[0084] See also Figure 6 , ammonia recovery and refining combined process, namely D-3, is a three-tower series connection to recover gas from the reaction effluent, purify liquid ammonia and remove impurities. Among them, the first-stage tower responsible for the separation of the main reaction product occupies 200-800% of the total reactor volume, with an operating pressure of 1.0-3.0Mpa and an operating temperature of 60-260℃. The second-stage tower occupies 150-500% of the total reactor volume, with an operating pressure of 0-0.5Mpa and an operating temperature of 10-200℃. The third-stage tower occupies 10-50% of the volume of the second tower, with an operating pressure of 1.0-3.0Mpa and an operating temperature of 0-180℃.

[0085] Example 1 (Complete Functional Design Case)

[0086] A complete functional design case includes the pilot plant module consisting of feed unit A, reactor unit B, distillation unit D, storage area E, auxiliary function area G, and utility F, as follows:

[0087]

[0088]

[0089]

[0090] Example 2 (typical combination case)

[0091] The pilot plant module consists of feed unit A, reactor unit B, main unit unit C, distillation unit D, product storage area E, auxiliary function area G, and public engineering F, as follows:

[0092]

[0093] Example 3 (reactor combination case)

[0094] When only the impact and performance of the reactor part need to be evaluated, the design of other units can be simplified, and the reactor unit can be expanded and specially structured.

[0095] The pilot plant reactor skid can be flexibly matched with 5 reaction units (B1~B5), (ref. Figure 3 ), the reactor composition and formula are as follows:

[0096]

[0097]

[0098] The pilot plant reactors in this example are illustrated using 5 combinations as an example, including but not limited to 5 and their different combinations.

Claims

1. An ethyleneamine pilot production system, characterized in that: It includes a feed unit (A), a reactor unit (B), a distillation unit (D), a storage area (E), an auxiliary functional area (G), and a utility project (F), which are separately assembled into skid-mounted modules and arranged in multiple layers.

2. The ethyleneamine pilot production system according to claim 1, characterized in that: The distillation tower (D1) and tail gas purification tower (G1) skids are separate components.

3. The ethyleneamine pilot production system according to claim 1, characterized in that: The reaction unit (B) is composed of a main reactor (1), a secondary reactor (2), an auxiliary reactor (3), a first functional reactor (4) and a second functional reactor (5) which are coupled to each other.

4. The ethyleneamine pilot production system according to claim 3, characterized in that: The feeding unit module (A) is a mixed feed of MEA / NH3 / H2 or a separate feed. The reactor module (B) is a reactor. The internal components of the reactor are: MEA 20-60%, NH3 40-80%, H2 0-5% (by weight wt%). The distillation tower module (D) is a distillation tower for recovering ammonia, Vd / VR=4:1-10:1, operating pressure 1.6-2.6Mpa, working temperature 60-240°C, RR=2-4.

5. The pilot production system of ethyleneamine according to claim 3, characterized in that: The secondary reactor (2) is a supplementary extension of the main reactor (1). The secondary reactor (2) is 30% to 150% of the volume of the main reactor (1), with an operating pressure of 10 to 30 MPa and a working temperature of 50 to 300°C.

6. The ethyleneamine pilot production system according to claim 3, characterized in that: The auxiliary reactor (3) is 40% to 80% of the volume of the main reactor (1), with an operating pressure of 10 to 40 MPa and a working temperature of 80 to 260°C.

7. The ethyleneamine pilot production system according to claim 3, characterized in that: The reaction raw materials of the main reactor (1), the secondary reactor (2), the auxiliary reactor (3), the first functional reactor (4) and the second functional reactor (5) provide compounds for hydrogenation reaction under the conditions of hydroamination reaction, wherein the raw materials include but are not limited to monoethanolamine, ammonia and hydrogen, which are added to the main reactor (1), the secondary reactor (2), the auxiliary reactor (3), the first functional reactor (4) and the second functional reactor (5) respectively before the reaction so that the reactors are in a hydrogen atmosphere, the amount of hydrogen used is 0.50-5.0% by weight of the monomers, the monoethanolamine feed ratio accounts for 20-80% of the total feed composition, and the ammonia feed ratio accounts for 20-80% of the total feed composition.

8. The ethyleneamine pilot production system according to claim 3, characterized in that: The first functional reactor (4) and the second functional reactor (5) are used to produce functional ethyleneamine products. The first functional reactor (4) and the second functional reactor (5) are connected in parallel or in series. In addition to monoethanolamine, ammonia and hydrogen, the feed composition also includes functional monomers, one or a combination of two or more of ethylenediamine, aminoethylethanolamine, diethanolamine, hydroxyethylpiperazine, diethylenetriamine and ethylene oxide. The feed ratio of the functional monomers accounts for 20-100% of the total feed composition. Among the various functional monomer feeds, ethylenediamine accounts for 0-100% of the total feed composition, aminoethylethanolamine accounts for 0-50% of the total feed composition, diethanolamine accounts for 0-15% of the total feed composition, hydroxyethylpiperazine accounts for 0-20% of the total feed composition, diethylenetriamine accounts for 0-60% of the total feed composition, and ethylene oxide accounts for 0-30% of the total feed composition.

9. The ethyleneamine pilot production system according to claim 1, characterized in that: The distillation unit (D) includes a single flash process (D-1), a flash and stripping combined process (D-2), and an ammonia recovery and refining combined process (D-3).

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