Production method and application of polyethylene polyamine

Abstract

The invention discloses a production method and application of polyethylene polyamine, and the production method comprises the following steps: 1) reacting ethylene glycol, ammonia and hydrogen to obtain a reaction product; 2) sequentially carrying out gas-liquid separation treatment, deamination treatment, dehydration treatment and heavy component removal treatment on the reaction product to obtain a heavy product and a light product; (3) sequentially carrying out ethanediamine separation treatment, piperazine separation treatment and ethanolamine separation treatment on the light product to respectively obtain ethanediamine, piperazine and ethanolamine; the heavy product is subjected to diethylenetriamine separation treatment, aminoethyl piperazine separation treatment and hydroxyethyl ethylenediamine separation treatment in sequence, and diethylenetriamine, aminoethyl piperazine and hydroxyethyl ethylenediamine are obtained respectively. The polyethylene polyamine production method provided by the invention has the characteristics of simple process flow, low raw material loss and low energy consumption.

Description

Technical Field

[0001] The invention relates to a production method of polyethylene polyamines, in particular to a production method of polyethylene polyamines and application thereof, belonging to the field of applied chemical industry. Background Art

[0002] Polyethylene polyamine is a general term for organic amine fine chemical products, mainly including linear amine compounds such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, and cyclic amine compounds such as piperazine, aminoethylpiperazine, and hydroxyethylpiperazine. Polyethylene polyamine is an important organic chemical raw material and fine chemical product, widely used in the production of chelating agents, emulsifiers, adhesives, medicines, pesticides, surfactants, epoxy resin curing agents, ion exchange resins, etc.

[0003] At present, the production routes of polyethylene polyamines can be divided into the ethylene dichloride method and the ethanolamine method according to the raw materials. The ethylene dichloride method is gradually being eliminated due to the high energy consumption in the production process, serious equipment corrosion, high investment cost, and serious environmental pollution caused by "three wastes". The ethanolamine method has the advantages of low energy consumption, low pollution, and high value-added by-products. This process is suitable for large-scale continuous production of clean processes and has strong competitiveness. At present, many European and American companies have adopted this technology. It is worth noting that the raw material of ethanolamine is ethylene oxide, which is restricted by the petrochemical industry.

[0004] As we all know, my country's energy structure is characterized by rich coal, poor oil and little gas. The synthesis of polyethylene polyamines using ethanolamine as raw material does not conform to my country's resource distribution. In recent years, the rapid development of coal-to-ethylene glycol has led to an overcapacity of ethylene glycol. Therefore, the study of ethylene glycol amination to produce polyethylene polyamines can not only solve the overcapacity of ethylene glycol, but also be conducive to the healthy development of the coal-to-ethylene glycol industry. Patent CN102233272A discloses a solid catalyst for catalyzing the amination of ethylene glycol to produce ethylenediamine. Under certain reaction conditions, the ethylene glycol conversion rate can be increased to 68%, the ethylenediamine selectivity is 78%, and the selectivity of other products with high added value is low. Patent CN102091641 discloses a supported silver cobalt or silver nickel reduction amination catalyst. Under the reaction conditions of 230°C, 20MPa, 55L / h hydrogen flow rate, and 40g / h liquid ammonia flow rate, the ethylene glycol conversion rate can be increased to 90%, the selectivity of ethylenediamine is 65.4%, the selectivity of ethanolamine is 24.2%, and the selectivity of piperazine and piperazine derivatives is 8.3%. It also faces the problems of low selectivity of high value-added products and harsh reaction conditions. Patent CN101384542 discloses a method for producing ethyleneamine and ethanolamine from ethylene glycol. It uses a two-stage reaction process. The first stage can use a known catalyst, and the second stage uses a catalyst mainly composed of Ru and Co. Under the reaction conditions of pressure 20MPa and temperature 150-170°C, the maximum conversion rate of ethylene glycol is 46%. It can be seen that the products produced by ethylene glycol amination are mainly ethylenediamine, and diethylenetriamine, piperazine, aminoethylpiperazine, and hydroxyethylpiperazine with high added value cannot be produced in large quantities. On the one hand, ethylene glycol needs to undergo two-step amination reactions to generate polyethylene polyamines, and its single-pass conversion rate is low and needs to be further improved. On the other hand, the reaction product is a mixture of multiple substances, including ethylenediamine, diethylenetriamine, hydroxyethylethylenediamine, piperazine, aminoethylpiperazine, aminoethylpiperazine, water, and unreacted ethylene glycol and ammonia, which require separation and purification to obtain a high-purity target product. In addition, most of the currently disclosed patents focus on high-efficiency catalysts, and there is no report on the process of preparing polyethylene polyamines by amination of ethylene glycol.

[0005] The ethylene glycol method for producing polyethylene polyamines is highly competitive, but there are still some problems to be solved in terms of industrial application. For example, most of the currently published patents focus on high-efficiency catalysts, but there are no reports on process research; multiple reactors are required to be connected in series to increase the conversion rate of ethylene glycol; the combined production of multiple polyethylene polyamine products requires many process steps; the proportion of ethylenediamine in polyethylene polyamine products is relatively high, and the proportion of other products with tighter market demand is relatively small. If these problems cannot be effectively solved, the production of polyethylene polyamines by the ethylene glycol method will face problems such as high equipment investment, long process flow, and high energy consumption, which can greatly reduce the process economy.

[0006] Therefore, developing a production method for polyethylene polyamines with a simple process flow, low raw material loss and low energy consumption has become a research direction in this field. Summary of the invention

[0007] The invention provides a method for producing polyethylene polyamines, which has the characteristics of short process flow, low raw material loss and low energy consumption.

[0008] The invention also provides a production device for polyethylene polyamines, which has the characteristics of low investment, low raw material loss and low energy consumption.

[0009] The present invention provides a method for producing polyethylene polyamines, which comprises the following steps:

[0010] 1) reacting ethylene glycol, ammonia and hydrogen to obtain a reaction product;

[0011] 2) sequentially subjecting the reaction product to gas-liquid separation, deammoniation, dehydration, and heavy removal treatments to obtain a heavy product and a light product;

[0012] 3) sequentially performing ethylenediamine separation treatment, piperazine separation treatment, and ethanolamine separation treatment on the light product to obtain ethylenediamine, piperazine, and ethanolamine, respectively;

[0013] The heavy product is sequentially subjected to diethylenetriamine separation treatment, aminoethylpiperazine separation treatment, and hydroxyethylethylenediamine separation treatment to obtain diethylenetriamine, aminoethylpiperazine, and hydroxyethylethylenediamine, respectively.

[0014] The production method as described above, wherein the reaction temperature of the reaction of ethylene glycol, ammonia and hydrogen is 150-300° C. and the reaction pressure is 5-20 MPa; and / or,

[0015] The molar ratio of ethylene glycol to ammonia is 1:(10-50); and / or,

[0016] The liquid phase volume space velocity of ethylene glycol is 0.1~1h -1 .

[0017] The production method as described above, wherein, in step 1), before allowing ethylene glycol, ammonia and hydrogen to react, further comprises subjecting ethylene glycol, ammonia and hydrogen to a heat exchange treatment, wherein the treatment temperature of the heat exchange treatment is 150-180° C. and the treatment pressure is 5-20 MPa.

[0018] The production method as described above, wherein the gas-liquid separation process is performed using a gas-liquid separator; and / or,

[0019] The deamination treatment is carried out using a deamination tower, wherein the operating pressure of the deamination tower is 0.1-5 MPa, the operating temperature of the tower top is 20-150° C., and the operating temperature of the tower bottom is 120-300° C.; and / or,

[0020] The dehydration treatment is performed using a dehydration tower, wherein the operating pressure of the dehydration tower is 5 to 500 kPa, the operating temperature of the tower top is 20 to 150° C., and the operating temperature of the tower bottom is 120 to 300° C.; and / or,

[0021] The deweighting treatment is carried out using a deweighting tower, the operating pressure of the deweighting tower is 5-300 kPa, the operating temperature of the tower top is 20-200°C, and the operating temperature of the tower bottom is 120-300°C.

[0022] The production method as described above, wherein the ethylenediamine separation treatment is carried out using an ethylenediamine separation tower, the operating pressure of the ethylenediamine separation tower is 5 to 300 kPa, the tower top operating temperature is 20 to 150° C., and the tower bottom operating temperature is 50 to 250° C.; and / or,

[0023] The piperazine separation treatment is carried out using a piperazine separation tower, wherein the operating pressure of the piperazine separation tower is 5 to 300 kPa, the tower top operating temperature is 20 to 250° C., and the tower bottom operating temperature is 50 to 300° C.; and / or,

[0024] The ethanolamine separation treatment is carried out using an ethanolamine separation tower, wherein the operating pressure of the ethanolamine separation tower is 5-100 kPa, the operating temperature of the tower top is 50-250° C., and the operating temperature of the tower bottom is 50-300° C.

[0025] The production method as described above, wherein a diethylenetriamine separation tower is used for diethylenetriamine separation treatment, the operating pressure of the diethylenetriamine separation tower is 5-100 kPa, the operating temperature of the tower top is 50-250° C., and the operating temperature of the tower bottom is 50-300° C.; and / or,

[0026] Using an aminoethylpiperazine separation tower to separate aminoethylpiperazine, the aminoethylpiperazine separation tower has an operating pressure of 5 to 100 kPa, a tower top operating temperature of 50 to 250° C., and a tower bottom operating temperature of 50 to 300° C.; and / or,

[0027] A hydroxyethylethylenediamine separation tower is used for hydroxyethylethylenediamine separation treatment. The operating pressure of the hydroxyethylethylenediamine separation tower is 5-100 kPa, the operating temperature of the tower top is 50-250° C., and the operating temperature of the tower bottom is 50-300° C.

[0028] The present invention also provides a production device for polyethylene polyamines for performing any of the above production methods, wherein the device comprises a hydrogen-ammonia heat exchanger, an ethylene glycol heat exchanger, a reactor, a gas-liquid separator, a deammoniation tower, a dehydration tower, a weight removal tower, an ethylenediamine separation tower, a piperazine separation tower, an ethanolamine separation tower, a diethylenetriamine separation tower, an aminoethylpiperazine separation tower, and a hydroxyethylethylenediamine separation tower;

[0029] The reactor is provided with N raw material inlets, N≥1, and the logistics outlet of the hydrogen and ammonia heat exchanger and the logistics outlet of the ethylene glycol heat exchanger are respectively connected to the raw material inlet of the reactor;

[0030] The logistics outlet of the reactor is connected to the logistics inlet of the gas-liquid separator;

[0031] The liquid phase logistics outlet of the gas-liquid separator is communicated with the logistics inlet of the deamination tower;

[0032] The tower bottom logistics outlet of the deamination tower is connected to the logistics inlet of the dehydration tower;

[0033] The tower bottom logistics outlet of the dehydration tower is connected with the logistics inlet of the deweight removal tower;

[0034] The top logistics outlet of the deweighting tower is connected to the logistics inlet of the ethylenediamine separation tower;

[0035] The tower bottom logistics outlet of the ethylenediamine separation tower is connected to the logistics inlet of the piperazine separation tower;

[0036] The tower bottom logistics outlet of the piperazine separation tower is connected to the logistics inlet of the ethanolamine separation tower;

[0037] The tower bottom logistics outlet of the deweighting tower is connected to the logistics inlet of the diethylenetriamine separation tower;

[0038] The tower bottom logistics outlet of the diethylenetriamine separation tower is connected to the logistics inlet of the aminoethylpiperazine separation tower;

[0039] The tower bottom logistics outlet of the aminoethylpiperazine separation tower is connected to the logistics inlet of the hydroxyethylethylenediamine separation tower;

[0040] The gas phase logistics outlet of the gas-liquid separator and the tower top logistics outlet of the deamination tower are respectively connected to the logistics inlet of the hydrogen-ammonia heat exchanger;

[0041] The tower bottom logistics outlet of the ethanolamine separation tower is communicated with the logistics inlet of the ethylene glycol heat exchanger.

[0042] The device as described above, wherein the reactor comprises:

[0043] A shell (110) having a containing cavity (111), a gas feed port (112) being arranged at the top end of the shell (110), a plurality of liquid feed ports (113) and a plurality of first discharge ports (114) being arranged at the side wall of the shell (110), and a second discharge port (115) being arranged at the bottom end of the shell (110);

[0044] a plurality of reaction beds (120), the plurality of reaction beds (120) being arranged at intervals along the height direction of the shell (110), the number of the reaction beds (120) being the same as the number of the liquid feed ports (113), and the plurality of liquid feed ports (113) being configured to provide liquid raw materials to the plurality of reaction beds (120) in a one-to-one correspondence;

[0045] a plurality of discharge pipelines (130), the plurality of discharge pipelines (130) being connected to the plurality of reaction beds (120) in a one-to-one correspondence, each of the discharge pipelines (130) comprising a first branch pipe (132) and a second branch pipe (133), the first branch pipes (132) of the plurality of discharge pipelines (130) being connected to the plurality of first discharge ports (114) in a one-to-one correspondence, the second branch pipe (133) of the discharge pipeline (130) connected to the upstream reaction bed (120) being configured to provide raw materials to the downstream reaction bed (120), and the second branch pipe (133) of the discharge pipeline (130) connected to the most downstream reaction bed (120) being connected to the second discharge port (115);

[0046] Each of the reaction beds (120) comprises a plurality of reaction tubes (121), the plurality of reaction tubes (121) of the reaction bed (120) are located at the same height and arranged in parallel with each other, each of the reaction tubes (121) is respectively connected to the discharge pipeline (130), and each of the reaction tubes (121) contains a catalyst (122);

[0047] The discharge pipeline (130) further comprises a main pipe (131) and a plurality of third branch pipes (134); the plurality of third branch pipes (134) are respectively connected to one end of the main pipe (131); the first branch pipe (132) and the second branch pipe (133) are respectively connected to the other end of the main pipe (131); and one end of the plurality of third branch pipes (134) away from the main pipe (131) is connected to the plurality of reaction tubes (121) in a one-to-one correspondence.

[0048] The device as described above, wherein a gas-liquid distributor (140) is disposed on the top of each of the reaction beds (120), and the gas-liquid distributor (140) is configured to transport raw materials to the multiple reaction tubes (121) of the reaction bed (120);

[0049] The gas-liquid distributor (140) comprises a first bottom plate (141), a second bottom plate (142), and a plurality of downcomers (143) located between the first bottom plate (141) and the second bottom plate (142), wherein the first bottom plate (141) and the second bottom plate (142) are respectively fixed to the shell (110);

[0050] The first bottom plate (141) is provided with a plurality of first through holes, the plurality of first through holes are connected to the plurality of downcomers (143) in a one-to-one correspondence, and one end of the plurality of downcomers (143) away from the first bottom plate (141) is connected to the plurality of reaction tubes (121) in a one-to-one correspondence.

[0051] The device as described above, wherein the reactor further comprises a plurality of liquid distribution pipes (150), the plurality of liquid distribution pipes (150) are connected to the plurality of liquid feed ports (113) in a one-to-one correspondence, and the liquid distribution pipes (150) are provided with a plurality of spray holes;

[0052] The liquid distribution pipe (150) comprises a main path (151) and a plurality of branch paths (152); one end of the main path (151) is connected to the liquid feed port (113); the plurality of branch paths (152) are respectively connected to the side walls of the main path (151); and the main path (151) and each of the branch paths (152) are respectively provided with a plurality of spray holes;

[0053] A pressure monitoring unit (161) and a temperature monitoring unit (162) are respectively installed on the side wall of the shell (110) at positions corresponding to the reaction beds (120).

[0054] The production method of polyethylene polyamines provided by the invention has the characteristics of short process flow, low raw material loss and low energy consumption. BRIEF DESCRIPTION OF THE DRAWINGS

[0055] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced one by one below. Obviously, the drawings in the following description are some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative labor.

[0056] Figure 1 A structural diagram of a production device for the first polyethylene polyamine provided by the present invention;

[0057] Figure 2 The present invention provides a first polyethylene polyamine production device used in the reactor structure diagram.

[0058] Description of reference numerals:

[0059] A1-Hydrogen and ammonia heat exchanger;

[0060] A2-ethylene glycol heat exchanger;

[0061] B-reactor;

[0062] C-gas-liquid separator;

[0063] D-deamination tower;

[0064] E-dehydration tower;

[0065] F-deweighting tower;

[0066] G-ethylenediamine separation tower;

[0067] H-piperazine separation column;

[0068] I-ethanolamine separation tower;

[0069] J-diethylenetriamine separation tower;

[0070] K-aminoethylpiperazine separation tower;

[0071] L-Hydroxyethylethylenediamine separation tower;

[0072] 1- Wastewater;

[0073] 2-Ethylenediamine products;

[0074] 3-Piperazine products;

[0075] 4-Ethanolamine products;

[0076] 5-Ethylene glycol;

[0077] 6-Diethylenetriamine products;

[0078] 7-aminoethylpiperazine products;

[0079] 8-Hydroxyethylethylenediamine products;

[0080] 9-Mixed amines and oligomers;

[0081] 110-shell; 111-accommodating chamber; 112-gas feed port; 113-liquid feed port; 114-first discharge port; 115-second discharge port;

[0082] 120-reaction bed; 121-reaction tube; 122-catalyst;

[0083] 130-discharging pipeline; 131-main pipe; 132-first branch pipe; 133-second branch pipe; 134-third branch pipe;

[0084] 140-gas-liquid distributor; 141-first bottom plate; 142-second bottom plate; 143-downcomer;

[0085] 150-liquid distribution pipe; 151-main line; 152-branch line;

[0086] 161-pressure monitoring unit; 162-temperature monitoring unit. DETAILED DESCRIPTION

[0087] In order to enable those skilled in the art to better understand the scheme of the present invention, the present invention is further described in detail below. The specific implementation methods listed below are only for describing the principles and features of the present invention. The examples are only used to explain the present invention and are not intended to limit the scope of the present invention. Based on the embodiments of the present invention, all other implementation methods obtained by ordinary technicians in the field without creative work are within the scope of protection of the present invention.

[0088] The first aspect of the present invention provides a method for producing polyethylene polyamines, the method comprising the following steps:

[0089] 1) reacting ethylene glycol, ammonia and hydrogen to obtain a reaction product;

[0090] 2) sequentially subjecting the reaction products to gas-liquid separation, deammoniation, dehydration, and heavy removal treatments to obtain heavy products and light products;

[0091] 3) Sequentially performing ethylenediamine separation treatment, piperazine separation treatment, and ethanolamine separation treatment on the light product to obtain ethylenediamine, piperazine, and ethanolamine, respectively;

[0092] The heavy product is sequentially subjected to diethylenetriamine separation treatment, aminoethylpiperazine separation treatment, and hydroxyethylethylenediamine separation treatment to obtain diethylenetriamine, aminoethylpiperazine, and hydroxyethylethylenediamine, respectively.

[0093] The preparation method of polyethylene polyamine provided by the present invention uses ethylene glycol, ammonia and hydrogen as raw materials, reacts in the presence of a catalyst, and obtains reaction products including ammonia (NH3), hydrogen (H2), water (H2O), ethanolamine (MEA), ethylenediamine (EDA), diethylenetriamine (DETA), hydroxyethylethylenediamine (AEEA), piperazine (PIP), aminoethylpiperazine (AEP), oligomers and unreacted ethylene glycol (EG).

[0094] The present invention does not limit the catalyst, reactor type and reaction conditions used for the reaction of ethylene glycol, ammonia and hydrogen. Common catalysts, reactors and reaction conditions in the art can be used as long as the requirements for obtaining the reaction products of the above components are met. In one embodiment, a metal oxide catalyst is used, a multi-stage fixed bed tubular reactor is used, and the above three substances are reacted under the reaction conditions of a reaction temperature of 200° C. and a reaction pressure of 8 MPa to obtain a reaction product.

[0095] The reaction product is subjected to gas-liquid separation treatment to obtain a gas phase mixture and a liquid phase mixture. The gas phase mixture includes unreacted ammonia and hydrogen, and the liquid phase mixture includes water, ethanolamine, ethylenediamine, diethylenetriamine, hydroxyethylethylenediamine, piperazine, aminoethylpiperazine, oligomers and unreacted ethylene glycol. The unreacted ammonia and hydrogen in the gas phase mixture can be used as raw materials to react with ethylene glycol again, and the liquid phase mixture is subjected to deamination treatment.

[0096] The present invention does not limit the type of reactor and reaction conditions used in the gas-liquid separation process. Common reactors and reaction conditions in the art can be used as long as the requirements for obtaining the gas phase mixture and liquid phase mixture of the above components are met.

[0097] The liquid phase mixture is subjected to deamination treatment to obtain ammonia gas and a liquid phase deamination treatment product, wherein the ammonia gas can be used as a raw material to react with hydrogen gas and ethylene glycol again, and the deamination treatment product is subjected to dehydration treatment.

[0098] The present invention does not limit the type of reactor and reaction conditions used in the deamination treatment. Common reactors and reaction conditions in the art can be used as long as the requirements for obtaining ammonia gas and deamination treatment products of the above components are met.

[0099] The deamination product is subjected to a dehydration treatment to remove water from the deamination product to obtain a dehydration product without water. The present invention does not limit the reactor type and reaction conditions used for the dehydration treatment, and common reactors and reaction conditions in the art can be used as long as the requirement of removing water from the deamination product is met.

[0100] The dehydration product is subjected to a de-heavy treatment, and the dehydration product is separated into a light component and a heavy component. The light component is a mixture including ethylenediamine, piperazine, ethanolamine and ethylene glycol, and the heavy component is a mixture including diethylenetriamine, aminoethylpiperazine and hydroxyethylethylenediamine. The present invention does not limit the reactor form and reaction conditions used for the de-heavy treatment, and common reactors and reaction conditions in the art can be used, as long as the requirements for obtaining the light component and the heavy component of the above-mentioned components are met. In one embodiment, a distillation tower can be used to carry out a de-heavy treatment on the dehydration product, and the boiling point difference of different components contained in the dehydration product is utilized to control the treatment conditions, and the light component and the heavy component are obtained at the top of the tower and the bottom of the tower, respectively.

[0101] The light component is subjected to ethylenediamine separation treatment, and ethylenediamine can be separated from the light component, and an ethylenediamine separation treatment product can be obtained at the same time. The present invention does not limit the reactor type and reaction conditions used in the ethylenediamine separation treatment, and common reactors and reaction conditions in the art can be used as long as the requirements of obtaining ethylenediamine and the ethylenediamine separation treatment product are met.

[0102] The ethylenediamine separation product is subjected to piperazine separation treatment, and piperazine can be separated from the ethylenediamine separation product, and a piperazine separation product containing ethanolamine and ethylene glycol can be obtained. The present invention does not limit the reactor type and reaction conditions used in the piperazine separation treatment, and common reactors and reaction conditions in the art can be used as long as the requirements of obtaining piperazine and the piperazine separation product are met.

[0103] The piperazine separation product can be subjected to ethanolamine separation treatment to separate the ethanolamine and ethylene glycol contained therein. The ethanolamine can be produced as a product, and the ethylene glycol can be recovered as a raw material.

[0104] The heavy component is subjected to diethylenetriamine separation treatment, and diethylenetriamine and a diethylenetriamine separation treatment product can be separated from the heavy component. The present invention does not limit the reactor type and reaction conditions used for the diethylenetriamine separation treatment, and common reactors and reaction conditions in the art can be used as long as the requirements for obtaining diethylenetriamine and a diethylenetriamine separation treatment product are met.

[0105] The diethylenetriamine separation product is subjected to aminoethylpiperazine separation treatment, and aminoethylpiperazine and an aminoethylpiperazine separation product can be separated from the diethylenetriamine separation product. The present invention does not limit the reactor type and reaction conditions used in the diethylenetriamine separation treatment, and common reactors and reaction conditions in the art can be used as long as the requirements of obtaining aminoethylpiperazine and an aminoethylpiperazine separation product are met.

[0106] The aminoethylpiperazine separation product contains hydroxyethylethylenediamine, mixed amines and oligomers. The hydroxyethylethylenediamine contained in the aminoethylpiperazine separation product can be separated by subjecting the hydroxyethylethylenediamine separation product to hydroxyethylethylenediamine separation. The present invention does not limit the reactor form and reaction conditions used in the hydroxyethylethylenediamine separation process, and common reactors and reaction conditions in the art can be used as long as the requirement of obtaining hydroxyethylethylenediamine is met.

[0107] It can be understood that the above-mentioned ethylenediamine separation treatment, piperazine separation treatment, ethanolamine separation treatment, diethylenetriamine separation treatment, aminoethylpiperazine separation treatment and hydroxyethylethylenediamine separation treatment can all be carried out using a distillation tower, utilizing the difference in boiling points of different components contained in the material to be treated to control the treatment conditions and obtain different components at the top of the tower and the bottom of the tower, respectively.

[0108] The method for producing polyethylene polyamines provided by the present invention selects ethylene glycol and ammonia, which are inexpensive and widely available, as reaction raw materials, which can improve the process economy; at the same time, the process operation is flexible, and the reaction temperature, pressure, and raw material ratio parameters are controllable, which can effectively regulate the ethylene glycol conversion rate and the distribution of polyethylene polyamine products, and effectively reduce the complexity of subsequent separation processes and devices, shorten the process flow, and reduce energy consumption. Therefore, the method for producing polyethylene polyamines provided by the present invention has the characteristics of a short process flow, low raw material loss, and low energy consumption.

[0109] In one embodiment, the reaction temperature of ethylene glycol, ammonia and hydrogen is 150-300° C., the reaction pressure is 5-20 MPa, the molar ratio of ethylene glycol to ammonia is 1:(10-50), and the liquid phase volume space velocity of ethylenediamine is 0.1-1 h -1 When the above reaction conditions are met, the method for producing polyethylene polyamines provided by the present invention can improve the mass transfer efficiency of ethylene glycol, and further promote the advantages of converting ethylene glycol into high value-added polyethylene polyamine products.

[0110] Furthermore, in one embodiment, before reacting ethylene glycol, ammonia and hydrogen in step 1), the step further includes subjecting ethylene glycol, ammonia and hydrogen to heat exchange treatment, wherein the treatment temperature of the heat exchange treatment is 150-180° C. and the treatment pressure is 5-20 MPa. Providing the raw materials with a suitable temperature can make the reaction between ethylene glycol, ammonia and hydrogen have a higher reaction rate, so that the production method of polyethylene polyamines provided by the present invention has a higher efficiency.

[0111] Furthermore, in one embodiment, the method for producing polyethylene polyamines provided by the present invention uses a gas-liquid separator for gas-liquid separation treatment; further, it also includes using a deamination tower to deaminize the liquid phase mixture. The operating pressure of the deamination tower is 0.1-5MPa, the operating temperature of the tower top is 20-150°C, and the operating temperature of the tower bottom is 120-300°C. The above-mentioned treatment conditions can make the separation technology effect of ammonia dissolved in the liquid phase logistics more prominent.

[0112] Furthermore, the method for producing polyethylene polyamines provided by the present invention uses a dehydration tower to dehydrate the logistics after deammoniation treatment. The operating pressure of the dehydration tower is 5-500 kPa, the operating temperature of the tower top is 20-150° C., and the operating temperature of the tower bottom is 120-300° C. The above treatment conditions can make the water separation technology more effective.

[0113] Furthermore, the production method of polyethylene polyamine provided by the present invention uses a deweighting tower to deweight the dehydration product. The operating pressure of the deweighting tower is 5 to 300 kPa, the operating temperature of the tower top is 20 to 200° C., and the operating temperature of the tower bottom is 120 to 300° C. The above-mentioned processing conditions can make the light and heavy component separation technology more effective.

[0114] Furthermore, the production method of polyethylene polyamine provided by the present invention uses an ethylenediamine separation tower to separate the light component. The operating pressure of the ethylenediamine separation tower is 5 to 300 kPa, the operating temperature of the tower top is 20 to 150° C., and the operating temperature of the tower bottom is 50 to 250° C. The above-mentioned processing conditions can make the ethylenediamine separation technology more effective.

[0115] Furthermore, the method for producing polyethylene polyamines provided by the present invention uses a piperazine separation tower to perform piperazine separation treatment on the ethylenediamine separation treatment product, the operating pressure of the piperazine separation tower is 5 to 300 kPa, the tower top operating temperature is 20 to 250° C., and the tower bottom operating temperature is 50 to 300° C. The above treatment conditions can make the piperazine separation technology more effective.

[0116] Furthermore, the method for producing polyethylene polyamines provided by the present invention uses an ethanolamine separation tower to separate ethanolamine from the piperazine separation treatment product, the operating pressure of the ethanolamine separation tower is 5 to 100 kPa, the tower top operating temperature is 50 to 250° C., and the tower bottom operating temperature is 50 to 300° C. The above-mentioned treatment conditions can make the ethanolamine separation technology more effective.

[0117] In one embodiment, the production method of polyethylene polyamines provided by the present invention uses a diethylenetriamine separation tower to separate the heavy components from diethylenetriamine, the operating pressure of the diethylenetriamine separation tower is 5 to 100 kPa, the tower top operating temperature is 50 to 250° C., and the tower bottom operating temperature is 50 to 300° C. The above-mentioned processing conditions can make the diethylenetriamine separation technology more effective.

[0118] Furthermore, the method for producing polyethylene polyamines provided by the present invention uses an aminoethyl piperazine separation tower to separate and treat the product of diethylene triamine separation treatment, and the operating pressure of the aminoethyl piperazine separation tower is 5 to 100 kPa, the tower top operating temperature is 50 to 250° C., and the tower bottom operating temperature is 50 to 300° C. The above-mentioned treatment conditions can make the aminoethyl piperazine separation technology more effective.

[0119] Furthermore, the method for producing polyethylene polyamines provided by the present invention uses a hydroxyethylethylenediamine separation tower to separate the aminoethylpiperazine separation product into hydroxyethylethylenediamine. The operating pressure of the hydroxyethylethylenediamine separation tower is 5 to 100 kPa, the tower top operating temperature is 50 to 250° C., and the tower bottom operating temperature is 50 to 300° C. The above-mentioned treatment conditions can make the hydroxyethylethylenediamine separation technology more effective.

[0120] The second aspect of the present invention provides a device for producing polyethylene polyamines, which can be used to implement any of the above-mentioned methods for producing polyethylene polyamines.

[0121] Figure 1 The first polyethylene polyamine production device provided by the present invention is as follows: Figure 1 As shown, the device includes a hydrogen-ammonia heat exchanger A1, an ethylene glycol heat exchanger A2, a reactor B, a gas-liquid separator C, a deammoniation tower D, a dehydration tower E, a weight removal tower F, an ethylenediamine separation tower G, a piperazine separation tower H, an ethanolamine separation tower I, a diethylenetriamine separation tower J, an aminoethylpiperazine separation tower K, and a hydroxyethylethylenediamine separation tower L;

[0122] Reactor B is provided with N raw material inlets, N≥1, and the logistics outlet of hydrogen and ammonia heat exchanger A1 and the logistics outlet of ethylene glycol heat exchanger A2 are respectively connected to the raw material inlet of reactor B;

[0123] Reactor B has multiple logistics outlets on the side wall and the bottom, and the above logistics outlets are connected to the logistics inlet of the gas-liquid separator C;

[0124] The liquid phase logistics outlet of the gas-liquid separator C is connected to the logistics inlet of the deamination tower D;

[0125] The tower bottom logistics outlet of the deamination tower D is connected with the logistics inlet of the dehydration tower E;

[0126] The tower bottom logistics outlet of the dehydration tower E is connected with the logistics inlet of the deweight removal tower F;

[0127] The top stream outlet of the deweighting tower F is connected to the stream inlet of the ethylenediamine separation tower G;

[0128] The tower bottom logistics outlet of the ethylenediamine separation tower G is connected with the logistics inlet of the piperazine separation tower H;

[0129] The tower bottom logistics outlet of the piperazine separation tower H is connected with the logistics inlet of the ethanolamine separation tower I;

[0130] The bottom stream outlet of the deweighting tower F is connected to the stream inlet of the diethylenetriamine separation tower J;

[0131] The bottom stream outlet of the diethylenetriamine separation tower J is connected to the stream inlet of the aminoethylpiperazine separation tower K;

[0132] The bottom stream outlet of the aminoethylpiperazine separation tower K is connected to the stream inlet of the hydroxyethylethylenediamine separation tower L;

[0133] The gas phase logistics outlet of the gas-liquid separator C and the tower top logistics outlet of the deammonification tower D are respectively connected to the logistics inlet of the hydrogen-ammonia heat exchanger A1;

[0134] The bottom stream outlet of the ethanolamine separation tower I is communicated with the stream inlet of the ethylene glycol heat exchanger A2.

[0135] The hydrogen and ammonia heat exchanger A1 and the glycol heat exchanger A2 provided by the present invention use steam at a temperature of 160° C. as a heat exchange medium to perform heat exchange treatment on the above three raw materials. The treatment temperature and treatment pressure of the heat exchange treatment of each raw material can be referred to above and will not be repeated here.

[0136] The production device of polyethylene polyamines provided by the present invention does not limit the type of reactor B, and a commonly used reactor B in the art can be used, as long as it can react hydrogen, ammonia and ethylene glycol to generate a crude product including polyethylene polyamines. In one embodiment, the reactor B is provided with N (N≥1) raw material inlets, and the logistics outlet of the hydrogen-ammonia heat exchanger A1 and the logistics outlet of the ethylene glycol heat exchanger A2 can be connected to the same raw material inlet or to different raw material inlets. Furthermore, the present invention also does not limit the number of heat exchanger raw material inlets connected to the logistics outlet of the hydrogen-ammonia heat exchanger A1 and the logistics outlet of the ethylene glycol heat exchanger A2, and there may be one or more heat exchanger raw material inlets connected to the logistics outlet of the hydrogen-ammonia heat exchanger A1, and there may also be one or more heat exchanger raw material inlets connected to the logistics outlet of the ethylene glycol heat exchanger A2.

[0137] The present invention does not specifically limit the catalyst filled in the reactor B, and it only needs to satisfy the requirement that hydrogen, ammonia and ethylene glycol can react to generate a crude product including polyethylene polyamines. The reaction conditions for the reaction of hydrogen, ammonia and ethylene glycol in the reactor B can be referred to above and will not be repeated here.

[0138] The gas-liquid separator C is used to perform gas-liquid separation on the reaction product to obtain a gas phase mixture and a liquid phase mixture. The gas-liquid separator C is provided with a gas phase logistics outlet at the top and a liquid phase logistics outlet at the bottom, wherein the gas phase logistics outlet is connected to the logistics inlet of the hydrogen-ammonia heat exchanger A1, and the gas phase mixture including hydrogen and ammonia is returned to the hydrogen-ammonia heat exchanger A1; the liquid phase logistics outlet is connected to the logistics of the deammonification tower D, and the liquid phase mixture is sent to the deammonification tower D for deammonification treatment. The treatment conditions of the gas-liquid separator C for gas-liquid separation of the reaction product can be referred to above and will not be repeated here.

[0139] The deamination tower D is used to deaminate the liquid mixture to obtain ammonia and liquid deammoniation products. The top of the deamination tower D is equipped with a cooler, the bottom of the tower is equipped with a reboiler, the tower body is provided with a logistics inlet, the top of the tower is provided with a tower top logistics outlet, and the bottom of the tower is provided with a tower bottom logistics outlet. The deammoniation product is produced at the tower bottom logistics outlet and transported to the dehydration tower E. The top logistics outlet is connected to the logistics inlet of the hydrogen-ammonia heat exchanger A1, and the produced ammonia is returned to the gas-ammonia heat exchanger. The treatment conditions of the deamination tower D when used for deamination treatment can be referred to above and will not be repeated here.

[0140] The dehydration tower E is used to dehydrate the deammoniation treatment product, remove the water in the deammoniation treatment product, and obtain a dehydrated treatment product without water. The top of the dehydration tower E is equipped with a cooler, the bottom of the tower is equipped with a reboiler, the tower body is provided with a logistics inlet, the top of the tower is provided with a tower top logistics outlet, and the bottom of the tower is provided with a tower bottom logistics outlet. The dehydrated water produced at the tower bottom logistics outlet is transported to the deweighting tower F, and the wastewater produced at the top logistics outlet enters the wastewater treatment system. The treatment conditions of the dehydration tower E when used for dehydration treatment can be referred to above and will not be repeated here.

[0141] The dehydration tower F is used to dehydrate the dehydrated product and separate the dehydrated product into light components and heavy components. The dehydration tower F is equipped with a cooler at the top, a reboiler at the bottom, a logistics inlet at the tower body, a top logistics outlet at the top, and a bottom logistics outlet at the bottom, wherein the light components are extracted from the top logistics outlet and transported to the ethylenediamine separation tower G, and the heavy components are extracted from the bottom logistics outlet and transported to the diethylenetriamine separation tower J for separation. The treatment conditions of the dehydration tower F for dehydration treatment can be referred to above and will not be repeated here.

[0142] The ethylenediamine separation tower G is used to separate the light components from ethylenediamine, and ethylenediamine is separated from the light components, and the ethylenediamine separation treatment product is obtained at the same time. The top of the ethylenediamine separation tower G is equipped with a cooler, the bottom of the tower is equipped with a reboiler, the tower body is provided with a logistics inlet, the top of the tower is provided with a tower top logistics outlet, and the bottom of the tower is provided with a tower bottom logistics outlet, wherein the tower top logistics outlet produces the target product ethylenediamine, and the bottom logistics outlet produces the ethylenediamine separation treatment product, and transports it to the piperazine separation tower H. The treatment conditions of the ethylenediamine separation tower G when used for ethylenediamine separation treatment can be referred to above, and will not be repeated here.

[0143] The piperazine separation tower H is used to perform piperazine separation treatment on the ethylenediamine separation treatment product, and piperazine is separated from the ethylenediamine separation treatment product, and a piperazine separation treatment product having components of ethanolamine and ethylene glycol is obtained at the same time. The piperazine separation tower H is equipped with a cooler at the top, a reboiler at the bottom, a logistics inlet at the tower body, a tower top logistics outlet at the top, and a tower bottom logistics outlet at the bottom, wherein the target product piperazine is extracted from the tower top logistics outlet, and the piperazine separation treatment product is extracted from the tower bottom logistics outlet and transported to the ethanolamine separation tower I. The treatment conditions of the piperazine separation tower H when used for piperazine separation treatment can be referred to above, and will not be repeated here.

[0144] The ethanolamine separation tower I is used to perform ethanolamine separation treatment on the piperazine separation treatment product, and separate the ethanolamine and ethylene glycol contained therein. The ethanolamine separation tower I is equipped with a cooler at the top, a reboiler at the bottom, a logistics inlet at the tower body, a tower top logistics outlet at the top, and a tower bottom logistics outlet at the bottom, wherein the target product ethanolamine is produced at the tower top logistics outlet, and ethylene glycol is produced at the tower bottom logistics outlet, and is transported to the logistics inlet of the ethylene glycol heat exchanger A2 for recycling as a reaction raw material.

[0145] The diethylenetriamine separation tower J is used to separate the diethylenetriamine from the heavy component, and diethylenetriamine and diethylenetriamine separation treatment products are separated from the heavy component. The diethylenetriamine separation tower J is equipped with a cooler at the top, a reboiler at the bottom, a logistics inlet at the tower body, a tower top logistics outlet at the top, and a tower bottom logistics outlet at the bottom, wherein the target product diethylenetriamine is produced from the tower top logistics outlet, and the diethylenetriamine separation treatment product is produced from the tower bottom logistics outlet and transported to the aminoethylpiperazine separation tower K. The treatment conditions of the diethylenetriamine separation tower J for diethylenetriamine separation treatment can be referred to above and will not be repeated here.

[0146] The aminoethylpiperazine separation tower K is used to separate the aminoethylpiperazine from the diethylenetriamine separation treatment product, and aminoethylpiperazine and the aminoethylpiperazine separation treatment product are separated from the diethylenetriamine separation treatment product. The aminoethylpiperazine separation tower K is equipped with a cooler at the top, a reboiler at the bottom, a logistics inlet at the tower body, a top logistics outlet at the top, and a bottom logistics outlet at the bottom, wherein the target product aminoethylpiperazine is produced at the top logistics outlet, and the aminoethylpiperazine separation treatment product is produced at the bottom logistics outlet, and transported to the hydroxyethylethylenediamine separation tower L. The treatment conditions of the aminoethylpiperazine separation tower K for aminoethylpiperazine separation can be referred to above, and will not be repeated here.

[0147] The aminoethylpiperazine separation treatment product contains hydroxyethylethylenediamine, mixed amines and oligomers. The hydroxyethylethylenediamine separation tower L is used to perform hydroxyethylethylenediamine separation treatment on the aminoethylpiperazine separation treatment product to separate the hydroxyethylethylenediamine contained therein. The hydroxyethylethylenediamine separation tower L is equipped with a cooler at the top, a reboiler at the bottom, a logistics inlet at the tower body, a tower top logistics outlet at the top, and a tower bottom logistics outlet at the bottom, wherein the target product hydroxyethylethylenediamine is extracted from the tower top logistics outlet, and mixed amines and oligomers are extracted from the bottom, which are connected to the mixed amine and oligomer extraction pipeline.

[0148] The device provided by the invention has the characteristics of low investment, low raw material loss and low energy consumption.

[0149] Further, Figure 2 The structural diagram of the reactor in the device of the polyethylene polyamine production method provided by the present invention. Figure 2 As shown, the reactor B includes a shell 110, a plurality of reaction beds 120 and a plurality of discharge pipes 130. The shell 110 has a containing cavity 111, a gas feed port 112 is provided at the top of the shell 110, a plurality of liquid feed ports 113 and a plurality of first discharge ports 114 are provided on the side wall of the shell 110, and a second discharge port 115 is provided at the bottom of the shell 110. The first discharge ports 114 and the second discharge ports 115 of the reactor B are the logistics outlets of the reactor, which are respectively connected to the logistics inlet of the gas-liquid separator.

[0150] Further, the plurality of reaction beds 120 are arranged at intervals along the height direction of the shell 110, the number of the reaction beds 120 is the same as the number of the liquid feed ports 113, and the plurality of liquid feed ports 113 are configured to provide liquid raw materials to the plurality of reaction beds 120 in a one-to-one correspondence. The plurality of discharge pipelines 130 are connected to the plurality of reaction beds 120 in a one-to-one correspondence, each of the discharge pipelines 130 includes a first branch pipe 132 and a second branch pipe 133, and the first branch pipes 132 of the plurality of discharge pipelines 130 are connected to the plurality of first discharge ports 114 in a one-to-one correspondence. The second branch pipe 133 of the discharge pipeline 130 connected to the upstream reaction bed 120 is configured to provide raw materials to the downstream reaction bed 120, and the second branch pipe 133 of the discharge pipeline 130 connected to the most downstream reaction bed 120 is connected to the second discharge port 115.

[0151] Schematically, the gas feed port 112 of the shell 110 can be used to introduce ammonia and hydrogen, and the liquid feed port 113 of the shell 110 can be used to introduce ethylene glycol. Ammonia, hydrogen and ethylene glycol react in the reaction bed 120 to generate polyethylene polyamine. Among them, the number of reaction beds 120, the number of liquid feed ports 113 and the number of discharge pipelines 130 are the same and at least two, which is not limited here. This embodiment does not limit the size of the interval between two adjacent reaction beds 120, and those skilled in the art can set it as needed.

[0152] It is worth noting that the staff can control the amount of ethylene glycol introduced into the corresponding liquid feed port 113 according to different reaction beds 120, thereby controlling the ratio of gas raw materials to liquid raw materials in the reaction bed 120, and can also adjust the hydrogen partial pressure by adjusting the ratio of hydrogen and ammonia in the gas introduced into the gas feed port 112. The above settings can not only efficiently promote the reaction, but also effectively control the product composition distribution.

[0153] In one embodiment, the first branch pipe 132 and the second branch pipe 133 of each discharge pipeline 130 are respectively provided with a switch valve. When the switch valve on the first branch pipe 132 is opened and the switch valve on the second branch pipe 133 is closed, the product of the reaction bed 120 connected to the discharge pipeline 130 can flow out from the corresponding first discharge port 114; when the switch valve on the first branch pipe 132 is closed and the switch valve on the second branch pipe 133 is opened, the product of the upstream reaction bed 120 can flow to the top of the downstream reaction bed 120 and continue to participate in the reaction in the downstream reaction bed 120.

[0154] The reactor B provided in this embodiment is provided with a plurality of liquid feed ports 113, a plurality of first discharge ports 114 and a second discharge port 115 on the shell 110, and a plurality of reaction beds 120 are provided inside the shell 110. The plurality of liquid feed ports 113 can provide liquid raw materials to the plurality of reaction beds 120 one by one, and the flow direction of the products after the reaction of the reaction beds 120 can be controlled by adjusting the main material pipeline. The reactor B provided in this embodiment integrates the functions of many reactors B for synthesizing different types of polyethylene polyamine products from ethylene glycol into one reactor B, promotes the improvement of the synthesis efficiency of polyethylene polyamines, optimizes the cost, and increases the benefits. When producing polyethylene polyamines, it is not necessary to set up a plurality of reaction devices in series. The reactor B is flexible in operation. When working, it can adjust the ratio of liquid raw materials to gas raw materials for different reaction beds 120, and effectively regulate the conversion rate of ethylene glycol and the distribution of polyethylene polyamine products.

[0155] In one embodiment, if Figure 2 As shown, each reaction bed 120 includes a plurality of reaction tubes 121. The plurality of reaction tubes 121 of the reaction bed 120 are located at the same height and arranged in parallel with each other, and each reaction tube 121 is respectively connected to a discharge pipeline 130, and each reaction tube 121 contains a catalyst 122. The discharge pipeline 130 includes a main pipe 131 and a plurality of third branch pipes 134, the plurality of third branch pipes 134 are respectively connected to one end of the main pipe 131, the first branch pipe 132 and the second branch pipe 133 are respectively connected to the other end of the main pipe 131, and the plurality of third branch pipes 134 are connected to the plurality of reaction tubes 121 in a one-to-one correspondence at one end away from the main pipe 131.

[0156] Schematically, at the same height position of the shell 110, a plurality of reaction tubes 121 are arranged along the radial direction of the shell 110. Specifically, the plurality of reaction tubes 121 of the reaction bed 120 are arranged at equal intervals in the annular direction along the center of the shell 110, that is, the plurality of reaction tubes 121 of the reaction bed 120 are arranged in a plurality of concentric rings, and the plurality of reaction tubes 121 in each ring are arranged at equal intervals.

[0157] Figure 2 As shown, the plurality of reaction tubes 121 are connected to one end of the main tube 131 through the plurality of third branch tubes 134 , and the first branch tube 132 and the second branch tube 133 may be connected to the other end of the main tube 131 .

[0158] It should be noted that the catalysts 122 in the reaction tubes 121 of different reaction beds 120 may be the same or different, and those skilled in the art may set the catalysts 122 in the specific reaction tubes 121 as needed, which is not limited here. The sizes of the reaction tubes 121 of different reaction beds 120 may be the same or different, which is not limited here.

[0159] The above arrangement enables the reaction bed 120 to accommodate enough catalysts 122. The liquid raw materials react with the gas raw materials in the reaction tubes 121. The heat generated during the reaction can be discharged from the gaps between the reaction tubes 121, ensuring that the reaction bed 120 has sufficient reaction capacity.

[0160] In a specific embodiment, a gas-liquid distributor 140 is disposed on the top of each reaction bed 120 , and the gas-liquid distributor 140 is configured to transport raw materials to the multiple reaction tubes 121 of the reaction bed 120 .

[0161] The liquid feed port 113 is located above the gas-liquid distributor 140 on the corresponding reaction bed 120, and the ethylene glycol input from the liquid feed port 113 and the hydrogen and ammonia input from the gas feed port 112 are mixed above the reaction bed 120. Optionally, the gas-liquid distributor 140 is provided with a plurality of passages, and the number of the passages may be the same as the number of the reaction tubes 121 below the gas-liquid distributor 140, and the mixture of ethylene glycol, hydrogen and ammonia may be input into the reaction tubes 121 of the reaction bed 120 through the plurality of passages of the gas-liquid distributor 140.

[0162] By arranging the gas-liquid distributor 140 above the reaction bed 120 , it is prevented that the raw material mixture enters the gap between the reaction tubes 121 and reduces the conversion rate of ethylene glycol.

[0163] Specifically, if Figure 2 As shown, the gas-liquid distributor 140 includes a first bottom plate 141 , a second bottom plate 142 and a plurality of downcomers 143 located between the first bottom plate 141 and the second bottom plate 142 . The first bottom plate 141 and the second bottom plate 142 are fixed to the shell 110 , respectively.

[0164] The first bottom plate 141 is provided with a plurality of first through holes, which are connected to the plurality of downcomers 143 in a one-to-one correspondence, and one end of the plurality of downcomers 143 away from the first bottom plate 141 is connected to the plurality of reaction tubes 121 in a one-to-one correspondence.

[0165] Schematically, the number of downcomers 143 is the same as the number of reaction tubes 121 , and the multiple downcomers 143 are coaxially arranged with the multiple reaction tubes 121 . Figure 2 As shown, the top end of each downcomer 143 is fixed to the first bottom plate 141, and the bottom end is fixed to the second bottom plate 142. The first bottom plate 141 and the second bottom plate 142 can be fixed to the housing 110 by fastening with fasteners, bonding or welding, etc., which is not limited here.

[0166] Optionally, a plurality of first through holes are provided on the first bottom plate 141, a plurality of second through holes are provided on the second bottom plate 142, the top end of the downcomer 143 is communicated with the first through holes, and the bottom end of the downcomer 143 is communicated with the second through holes. It can be understood that the downcomer 143 serves as a passage of the gas-liquid distributor 140, and the mixture of ethylene glycol, hydrogen and ammonia can be input into the reaction tubes 121 of the reaction bed 120 through the downcomer 143, the first through holes on the first bottom plate 141 and the second through holes on the second bottom plate 142, so as to prevent the raw material mixture from entering the gaps between the reaction tubes 121.

[0167] Figure 2 As shown, the reactor B further includes a plurality of liquid distribution pipes 150 , which are connected to the plurality of liquid feed ports 113 in a one-to-one correspondence, and a plurality of spray holes are provided on the liquid distribution pipes 150 .

[0168] Schematically, one end of the liquid distribution pipe 150 is connected to the liquid feed port 113, and the ethylene glycol liquid enters the liquid distribution pipe 150 through the liquid feed port 113. The liquid in the liquid distribution pipe 150 can be sprayed from the spray hole in the liquid distribution pipe 150 to the inside of the accommodating chamber 111 to achieve full mixing of the liquid raw material and the gas raw material to ensure the conversion rate of ethylene glycol. This embodiment does not limit the number of spray holes and the specific positions of the spray holes on the liquid distribution pipe 150, and those skilled in the art can set them as needed.

[0169] Specifically, the liquid distribution pipe 150 includes a main passage 151 and a plurality of branches 152. One end of the main passage 151 is connected to the liquid feed port 113, and the plurality of branches 152 are respectively connected to the side walls of the main passage 151. The main passage 151 and each branch 152 are respectively provided with a plurality of spray holes.

[0170] Pipes may be used as the main path 151 and the branch paths 152 of the liquid distribution pipe 150, the extension direction of each branch path 152 may be perpendicular to the extension direction of the main path 151, and one end of the main path 151 away from the liquid feed port 113 may extend to a side of the housing 110 away from the liquid feed port 113. The ethylene glycol entering through the liquid feed port 113 may flow from the main path 151 to each branch path 152.

[0171] Through the above arrangement, the ethylene glycol in the main path 151 of the liquid distribution pipe 150 can be sprayed into the interior of the containing chamber 111 through the spray holes on the main path 151, and the ethylene glycol in each branch path 152 can be sprayed into the interior of the containing chamber 111 through the spray holes on the corresponding branch paths 152, thereby ensuring the spray range of the ethylene glycol liquid in the containing chamber 111, so that the liquid raw material can be further fully mixed with the gas raw material.

[0172] like Figure 2As shown, a pressure monitoring unit 161 and a temperature monitoring unit 162 are respectively installed on the side wall of the shell 110 at positions corresponding to each reaction bed 120 .

[0173] The detection end of the pressure monitoring unit 161 and the detection end of the temperature monitoring unit 162 are both directed toward the reaction tube 121 of the corresponding reaction bed 120. Schematically, a pressure sensor can be used as the pressure monitoring unit 161, and a temperature sensor can be used as the temperature monitoring unit 162. It can be understood that the pressure monitoring unit 161 can detect the pressure inside the shell 110 at the position of the reaction bed 120, and the temperature monitoring unit 162 can detect the temperature inside the shell 110 at the position of the reaction bed 120.

[0174] In this structure, the staff can obtain the pressure and temperature at different positions of the reaction bed 120 through the pressure monitoring unit 161 and the temperature monitoring unit 162, so as to control the pressure and temperature at the position of the reaction bed 120, on the one hand, ensuring that the environment at the position of the reaction bed 120 can make the reaction proceed smoothly, and on the other hand, the energy consumption of the reactor B can be controlled by the pressure and temperature at the position of the reaction bed 120. In addition, by regulating the temperature and pressure of the reaction, not only the reaction is efficiently promoted, but also the product composition distribution can be controlled.

[0175] Hereinafter, the production method and application of polyethylene polyamines provided by the present invention are described in detail through specific embodiments.

[0176] Example 1

[0177] In this embodiment, ethylene glycol, ammonia and hydrogen are used as raw materials. Figure 1 The device shown in the figure synthesizes polyethylene polyamine. Figure 1 Reactor B uses Figure 2 structure.

[0178] Specifically, the catalyst used is CuNiZrCeMn oxide, which can be prepared using the method provided in Example 1 of the Chinese patent publication number CN102233272A;

[0179] The reaction temperature of ethylene glycol, ammonia and hydrogen is 150-300°C and the reaction pressure is 5-20MPa;

[0180] The molar ratio of ethylene glycol to ammonia is 1:(10-50);

[0181] The liquid phase volume space velocity of ethylene glycol is 0.1~1h -1 ;

[0182] The treatment temperature of heat exchange treatment is 150-180℃, and the treatment pressure is 5-20MPa;

[0183] The operating pressure of deamination tower D is 0.1-5 MPa, the operating temperature of the tower top is 20-150°C, and the operating temperature of the tower bottom is 120-300°C;

[0184] The operating pressure of dehydration tower E is 5-500 kPa, the operating temperature of the tower top is 20-150°C, and the operating temperature of the tower bottom is 120-300°C;

[0185] The operating pressure of the deweighting tower F is 5-300 kPa, the operating temperature of the tower top is 20-200°C, and the operating temperature of the tower bottom is 120-300°C;

[0186] The operating pressure of the ethylenediamine separation tower G is 5-300 kPa, the operating temperature of the tower top is 20-150°C, and the operating temperature of the tower bottom is 50-250°C;

[0187] The operating pressure of the piperazine separation tower H is 5-300 kPa, the operating temperature of the tower top is 20-250°C, and the operating temperature of the tower bottom is 50-300°C;

[0188] The operating pressure of the ethanolamine separation tower I is 5-100 kPa, the operating temperature of the tower top is 50-250°C, and the operating temperature of the tower bottom is 50-300°C;

[0189] The operating pressure of the diethylenetriamine separation tower J is 5-100 kPa, the operating temperature of the tower top is 50-250°C, and the operating temperature of the tower bottom is 50-300°C;

[0190] The operating pressure of aminoethylpiperazine separation tower K is 5-100 kPa, the operating temperature of the tower top is 50-250°C, and the operating temperature of the tower bottom is 50-300°C;

[0191] The operating pressure of the hydroxyethylethylenediamine separation tower L is 5-100 kPa, the operating temperature of the tower top is 50-250°C, and the operating temperature of the tower bottom is 50-300°C.

[0192] The reaction results are shown in Table 1.

[0193] Table 1 Reaction product statistics

[0194]

[0195] From Table 1, we can see that using Figure 1 When the device shown synthesizes polyethylene polyamines, ethylene glycol has a higher conversion rate, and the products EDA, PIP, MEA, DETA, AEP, and AEEA all have higher product yields and product purities.

[0196] In the description of the embodiments of the present application, it should be noted that, unless otherwise clearly specified and limited, the terms "installed", "connected", and "connected" should be understood in a broad sense, for example, it can be a fixed connection, or it can be an indirect connection through an intermediate medium, it can be the internal connection of two elements or the interaction relationship between two elements. For ordinary technicians in this field, the specific meanings of the above terms in this application can be understood according to specific circumstances.

[0197] The terms "first", "second", "third", "fourth", etc. (if any) in the specification and claims of the present application and the above-mentioned drawings are used to distinguish similar objects, and are not necessarily used to describe a specific order or sequence. It should be understood that the data used in this way can be interchangeable where appropriate, so that the embodiments of the present application described herein can be implemented in an order other than those illustrated or described herein, for example. In addition, the terms "including" and "having" and any of their variations are intended to cover non-exclusive inclusions, for example, a process, method, system, product or device comprising a series of steps or units is not necessarily limited to those steps or units clearly listed, but may include other steps or units that are not clearly listed or inherent to these processes, methods, products or devices.

[0198] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it. Although the present invention has been described in detail with reference to the above embodiments, those skilled in the art should understand that the technical solutions described in the above embodiments can still be modified, or some or all of the technical features can be replaced by equivalents. However, these modifications or replacements do not deviate the essence of the corresponding technical solutions from the technical solutions of the embodiments of the present invention.

Claims

1. A method for producing polyethylene polyamines, characterized in that: The steps include: 1) reacting ethylene glycol, ammonia and hydrogen to obtain a reaction product; 2) sequentially subjecting the reaction product to gas-liquid separation, deammoniation, dehydration, and heavy removal treatments to obtain a heavy product and a light product; 3) sequentially subjecting the light product to ethylenediamine separation treatment, piperazine separation treatment, and ethanolamine separation treatment to obtain ethylenediamine, piperazine, and ethanolamine, respectively; The heavy product is sequentially subjected to diethylenetriamine separation treatment, aminoethylpiperazine separation treatment, and hydroxyethylethylenediamine separation treatment to obtain diethylenetriamine, aminoethylpiperazine, and hydroxyethylethylenediamine, respectively.

2. The method according to claim 1, characterized in that: The reaction temperature of ethylene glycol, ammonia and hydrogen is 150-300° C. and the reaction pressure is 5-20 MPa; and / or, The molar ratio of ethylene glycol to ammonia is 1:(10-50); and / or, The liquid phase volume space velocity of ethylene glycol is 0.1~1h -1 .

3. The method according to claim 1 or 2, characterized in that: In step 1), before the ethylene glycol, ammonia and hydrogen are reacted, the ethylene glycol, ammonia and hydrogen are subjected to heat exchange treatment, wherein the treatment temperature of the heat exchange treatment is 150-180° C. and the treatment pressure is 5-20 MPa.

4. The method according to any one of claims 1 to 3, characterized in that Using a gas-liquid separator to perform the gas-liquid separation process; and / or, The deamination treatment is carried out using a deamination tower, wherein the operating pressure of the deamination tower is 0.1-5 MPa, the operating temperature of the tower top is 20-150° C., and the operating temperature of the tower bottom is 120-300° C.; and / or, The dehydration treatment is performed using a dehydration tower, wherein the operating pressure of the dehydration tower is 5 to 500 kPa, the operating temperature of the tower top is 20 to 150° C., and the operating temperature of the tower bottom is 120 to 300° C.; and / or, The deweighting treatment is carried out using a deweighting tower, the operating pressure of the deweighting tower is 5-300 kPa, the operating temperature of the tower top is 20-200°C, and the operating temperature of the tower bottom is 120-300°C.

5. The method according to any one of claims 1 to 4, characterized in that The ethylenediamine separation treatment is carried out using an ethylenediamine separation tower, wherein the operating pressure of the ethylenediamine separation tower is 5 to 300 kPa, the tower top operating temperature is 20 to 150° C., and the tower bottom operating temperature is 50 to 250° C.; and / or, The piperazine separation treatment is carried out using a piperazine separation tower, wherein the operating pressure of the piperazine separation tower is 5 to 300 kPa, the tower top operating temperature is 20 to 250° C., and the tower bottom operating temperature is 50 to 300° C.; and / or, The ethanolamine separation treatment is carried out using an ethanolamine separation tower, wherein the operating pressure of the ethanolamine separation tower is 5-100 kPa, the operating temperature of the tower top is 50-250° C., and the operating temperature of the tower bottom is 50-300° C.

6. The method according to any one of claims 1 to 5, characterized in that Using a diethylenetriamine separation tower to separate diethylenetriamine, the operating pressure of the diethylenetriamine separation tower is 5-100 kPa, the tower top operating temperature is 50-250° C., and the tower bottom operating temperature is 50-300° C.; and / or, Using an aminoethylpiperazine separation tower to separate aminoethylpiperazine, the aminoethylpiperazine separation tower has an operating pressure of 5 to 100 kPa, a tower top operating temperature of 50 to 250° C., and a tower bottom operating temperature of 50 to 300° C.; and / or, A hydroxyethylethylenediamine separation tower is used for hydroxyethylethylenediamine separation treatment. The operating pressure of the hydroxyethylethylenediamine separation tower is 5-100 kPa, the operating temperature of the tower top is 50-250° C., and the operating temperature of the tower bottom is 50-300° C.

7. A production device for polyethylene polyamines for carrying out the production method according to any one of claims 1 to 6, characterized in that: The device comprises a hydrogen-ammonia heat exchanger, an ethylene glycol heat exchanger, a reactor, a gas-liquid separator, a deammoniation tower, a dehydration tower, a weight removal tower, an ethylenediamine separation tower, a piperazine separation tower, an ethanolamine separation tower, a diethylenetriamine separation tower, an aminoethylpiperazine separation tower, and a hydroxyethylethylenediamine separation tower; The reactor is provided with N raw material inlets, N≥1, and the logistics outlet of the hydrogen and ammonia heat exchanger and the logistics outlet of the ethylene glycol heat exchanger are respectively connected to the raw material inlet of the reactor; The logistics outlet of the reactor is connected to the logistics inlet of the gas-liquid separator; The liquid phase logistics outlet of the gas-liquid separator is communicated with the logistics inlet of the deamination tower; The tower bottom logistics outlet of the deamination tower is connected to the logistics inlet of the dehydration tower; The tower bottom logistics outlet of the dehydration tower is connected with the logistics inlet of the deweight removal tower; The top logistics outlet of the deweighting tower is connected to the logistics inlet of the ethylenediamine separation tower; The tower bottom logistics outlet of the ethylenediamine separation tower is connected to the logistics inlet of the piperazine separation tower; The tower bottom logistics outlet of the piperazine separation tower is connected with the logistics inlet of the ethanolamine separation tower; The tower bottom logistics outlet of the deweighting tower is connected to the logistics inlet of the diethylenetriamine separation tower; The tower bottom logistics outlet of the diethylenetriamine separation tower is connected to the logistics inlet of the aminoethylpiperazine separation tower; The tower bottom logistics outlet of the aminoethylpiperazine separation tower is connected to the logistics inlet of the hydroxyethylethylenediamine separation tower; The gas phase logistics outlet of the gas-liquid separator and the tower top logistics outlet of the deamination tower are respectively connected to the logistics inlet of the hydrogen-ammonia heat exchanger; The tower bottom logistics outlet of the ethanolamine separation tower is communicated with the logistics inlet of the ethylene glycol heat exchanger.

8. The device according to claim 7, characterized in that The reactor comprises: A shell (110) having a containing cavity (111), a gas feed port (112) being arranged at the top end of the shell (110), a plurality of liquid feed ports (113) and a plurality of first discharge ports (114) being arranged at the side wall of the shell (110), and a second discharge port (115) being arranged at the bottom end of the shell (110); a plurality of reaction beds (120), the plurality of reaction beds (120) being arranged at intervals along the height direction of the shell (110), the number of the reaction beds (120) being the same as the number of the liquid feed ports (113), and the plurality of liquid feed ports (113) being configured to provide liquid raw materials to the plurality of reaction beds (120) in a one-to-one correspondence; a plurality of discharge pipelines (130), the plurality of discharge pipelines (130) being connected to the plurality of reaction beds (120) in a one-to-one correspondence, each of the discharge pipelines (130) comprising a first branch pipe (132) and a second branch pipe (133), the first branch pipes (132) of the plurality of discharge pipelines (130) being connected to the plurality of first discharge ports (114) in a one-to-one correspondence, the second branch pipe (133) of the discharge pipeline (130) connected to the upstream reaction bed (120) being configured to provide raw materials to the downstream reaction bed (120), and the second branch pipe (133) of the discharge pipeline (130) connected to the most downstream reaction bed (120) being connected to the second discharge port (115); Each of the reaction beds (120) comprises a plurality of reaction tubes (121), the plurality of reaction tubes (121) of the reaction bed (120) are located at the same height and arranged in parallel with each other, each of the reaction tubes (121) is respectively connected to the discharge pipeline (130), and each of the reaction tubes (121) contains a catalyst (122); The discharge pipeline (130) further comprises a main pipe (131) and a plurality of third branch pipes (134); the plurality of third branch pipes (134) are respectively connected to one end of the main pipe (131); the first branch pipe (132) and the second branch pipe (133) are respectively connected to the other end of the main pipe (131); and one end of the plurality of third branch pipes (134) away from the main pipe (131) is connected to the plurality of reaction tubes (121) in a one-to-one correspondence.

9. The device according to claim 8, characterized in that A gas-liquid distributor (140) is disposed on the top of each of the reaction beds (120), and the gas-liquid distributor (140) is configured to transport raw materials to the multiple reaction tubes (121) of the reaction bed (120); The gas-liquid distributor (140) comprises a first bottom plate (141), a second bottom plate (142), and a plurality of downcomers (143) located between the first bottom plate (141) and the second bottom plate (142), wherein the first bottom plate (141) and the second bottom plate (142) are respectively fixed to the shell (110); The first bottom plate (141) is provided with a plurality of first through holes, the plurality of first through holes are connected to the plurality of downcomers (143) in a one-to-one correspondence, and one end of the plurality of downcomers (143) away from the first bottom plate (141) is connected to the plurality of reaction tubes (121) in a one-to-one correspondence.

10. The device according to claim 9, characterized in that The reactor further comprises a plurality of liquid distribution pipes (150), wherein the plurality of liquid distribution pipes (150) are connected to the plurality of liquid feed ports (113) in a one-to-one correspondence, and the liquid distribution pipes (150) are provided with a plurality of spray holes; The liquid distribution pipe (150) comprises a main path (151) and a plurality of branch paths (152); one end of the main path (151) is connected to the liquid feed port (113); the plurality of branch paths (152) are respectively connected to the side walls of the main path (151); and the main path (151) and each of the branch paths (152) are respectively provided with a plurality of spray holes; A pressure monitoring unit (161) and a temperature monitoring unit (162) are respectively installed on the side wall of the shell (110) at positions corresponding to the reaction beds (120).

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