CN110639605B

CN110639605B - Catalyst for increasing production of monoethanolamine and diethanolamine

Info

Publication number: CN110639605B
Application number: CN201810674895.5A
Authority: CN
Inventors: 刘师前; 钱斌; 刘仲能; 韩亚梅
Original assignee: China Petroleum and Chemical Corp; Sinopec Shanghai Research Institute of Petrochemical Technology
Current assignee: China Petroleum and Chemical Corp; Sinopec Shanghai Research Institute of Petrochemical Technology
Priority date: 2018-06-27
Filing date: 2018-06-27
Publication date: 2021-10-01
Anticipated expiration: 2038-06-27
Also published as: CN110639605A

Abstract

The invention relates to a catalyst for increasing the production of monoethanolamine and diethanolamine, which mainly solves the problems of byproduct Triethanolamine (TEA) and large energy consumption in product separation in the prior art when Monoethanolamine (MEA) and Diethanolamine (DEA) are produced, and provides the catalyst for increasing the production of monoethanolamine and diethanolamine.

Description

Catalyst for increasing production of monoethanolamine and diethanolamine

Technical Field

The invention relates to a catalyst for increasing the production of monoethanolamine and diethanolamine.

Background

Ethanolamine (EA) is a generic name of products in which hydrogen atoms in ammonia molecules are respectively substituted by one, two or three hydroxyethanol, and is respectively called Monoethanolamine (MEA), Diethanolamine (DEA) and Triethanolamine (TEA). The ethanolamine compound contains two functional groups: hydroxyl and amine groups, and therefore have certain chemical properties and novel properties of alcohols and amines. The characteristics and the interaction of the bifunctional groups enable the compound to become an important organic intermediate and a chemical end product, and the application is very wide. One of the applications of ethanolamine is to synthesize important basic raw materials of products such as surfactants, medicines, polyurethane aids, rubber processing aids, antifreeze aids and the like.

At present, the related enterprises engaged in ethanolamine production abroad mainly include Dow chemical, BASF company, Huntsman company, Nippon Shokubai company, and the like. Ethanolamine enterprises can be classified into four categories according to the concentration of ammonia in the raw material used: 1) american SD company adopts low-concentration ammonia water as a reaction raw material, EO, 20-30 wt% of ammonia water (including fresh materials and circulating materials) and circulating MEA are placed in a fixed bedReaction in the reactor (adjustment of the structure of the reaction product with MEA), NH₃EO is 10:1, the reaction temperature is 100 ℃, the system pressure is 0.5MPa, the products after the reaction are separated and rectified to respectively obtain high-purity MEA, DEA and TEA, the relative contents of the MEA, the DEA and the TEA are respectively 69 wt%, 21 wt% and 10 wt%, the excessive ammonia in the reaction system is recovered by reduced pressure distillation, and the residual ammonia is repeatedly circulated in the form of ammonia water. Because the water content in the system is high, the energy consumption is high in the process of reaction temperature rise and temperature reduction, and the product is easy to dissolve in water and has high dehydration energy consumption. Therefore, although the reaction conditions of the production method of low-concentration ammonia water are mild, the energy consumption is too high, and the production method is gradually eliminated. 2) Dow chemical company adopts medium-high concentration ammonia water as a reaction raw material, the concentration of the ammonia water is 35-50 wt%, the system pressure is 3.5MPa, and the reaction temperature is 115-130 ℃. Dow chemical company adopts the method of high vacuum flash distillation for the first time to retrieve the ammonia in the system, and the product distribution is adjusted by the content of raw material ammonia, and this company adopts the coproduction device of EO and ethanolamine in production. 3) BASF company adopts high-concentration ammonia water as raw material, the concentration of the ammonia water is more than 90 wt%, the system pressure is 10MPa, and NH is generated₃And (2) EO (ethylene oxide)/EO (ethylene oxide) is 15-25: 1, the residence time is 3-30 min, a four-stage heat-insulating pipe reactor is adopted, EO is placed at different nodes in batches and enters the reactor, the reacted materials are decompressed in a flash tower, most of ammonia is evaporated, ammonia is condensed into liquid ammonia and returns, residual ammonia is evaporated at 0.4MPa, and after the liquid ammonia is absorbed into dilute ammonia water by water in a dehydration tower, the dilute ammonia water and the liquid ammonia are prepared into 90% concentrated ammonia water to participate in the reaction. The adoption of high-concentration ammonia has become a trend of an ammonia water method process, and the ammonia water method can obtain a product with balanced composition, but has the problems of more by-products of the product, high separation difficulty, incapability of recovering reaction heat and the like. 4) Nippon Shokubai (Tsunekih, Moriya a, Baba h.us6169207; moriya a, Tsuneki h.ep0652207; moriya a, Tsuneki h.us 5880058; tsuneki H, Moriya a, Baba H.A EP 0941986; tsuneki H, Kirishiki M, Arita Y, Hashimoto Y, Oku T, Shindou H, Urano Y, morishitaf.us 6559342; tsuneki h. us6455016) company uses liquid ammonia as a raw material and La-modified zeolite as a catalyst to generate diethanolamine with high selectivity, and has been applied industrially. The process conditions are as follows: the reaction temperature is 100-120 ℃, the pressure is 12-15 MPa, and the liquid phase space velocity is 8-10 hr^-1When in use, a fixed bed reactor is adopted, and the single-pass weight selectivity of the diethanol amine is about 41 percent; by recycling monoethanolamine, the weight selectivity of diethanolamine can reach 81%, and ethylene oxide can be completely converted, but the product still contains about 7% of triethanolamine.

In recent years, the market demand of the market for products such as ethylenediamine, piperazine, triethylene diamine and the like is increased sharply, the yield increase of upstream products such as monoethanolamine and diethanolamine is obviously stimulated, the triethanolamine is co-produced in the prior art, and the separation and production cost can be greatly increased by separating the triethanolamine from the products and converting the triethanolamine into the monoethanolamine and the diethanolamine.

Disclosure of Invention

One of the technical problems to be solved by the invention is to provide a catalyst for increasing the production of monoethanolamine and diethanolamine, which has the advantages of high EO conversion rate, high total selectivity of monoethanolamine and diethanolamine and low selectivity of byproduct triethanolamine, and reduces the energy consumption for separating and converting triethanolamine into monoethanolamine and diethanolamine.

The second technical problem to be solved by the invention is a preparation method of the catalyst.

The invention also aims to solve the technical problem of application of the catalyst.

In order to solve one of the above technical problems, the technical solution of the present invention is as follows:

the catalyst for increasing the production of the monoethanolamine and the diethanolamine comprises a ZSM-11 molecular sieve and molecular sieve modification elements, wherein the modification elements comprise La and Ni.

La and Ni have synergistic effect in improving the conversion rate of EO and the selectivity of monoethanolamine and diethanolamine.

As a first preferred technical solution, the modifying element further preferably includes P. La and P have synergistic effect on the aspect of improving the selectivity of monoethanolamine and diethanolamine; ni and P have synergistic effect on the aspect of improving the selectivity of monoethanolamine and diethanolamine; meanwhile, La, Ni and P have ternary synergistic effect on the aspect of improving the selectivity of monoethanolamine and diethanolamine in the catalyst.

As a second preferred technical solution, the modifying element further preferably includes an alkali metal, and the alkali metal is preferably Na or K. La and alkali metal have synergistic effect on the aspect of improving the selectivity of monoethanolamine and diethanolamine; the alkali metal and Ni have a synergistic effect on the aspect of improving the selectivity of the monoethanolamine and the diethanolamine; meanwhile, La, alkali metal and Ni have ternary synergistic effect on the aspect of improving the selectivity of monoethanolamine and diethanolamine in the catalyst.

In the above technical solution, the ratio of La to the alkali metal is not particularly limited, and is, for example, 0.5 to 10 by weight, for example, but not limited to, 1.03, 1.53, 2.03, 2.53, 3.03, 3.53, 4.03, 4.53, 5.03, 5.53, 6.03, 7.03, 8.03, 9.03, and the like. For comparison, the ratio of 8.0 is commonly used in the embodiments of the present invention.

In the above technical solution, the ratio of La to P is not particularly limited, and is, for example, 0.5 to 10 by weight, for example, but not limited to, 1.03, 1.53, 2.03, 2.53, 3.03, 3.53, 4.03, 4.53, 5.03, 5.53, 6.03, 7.03, 8.03, 9.03, and the like. For comparison, the ratio of 8.0 is commonly used in the embodiments of the present invention.

In the above technical solution, the ratio of La to Ni is not particularly limited, and is, for example, 0.5 to 10 by weight, for example, but not limited to, 1.03, 1.53, 2.03, 2.53, 3.03, 3.53, 4.03, 4.53, 5.03, 5.53, 6.03, 7.03, 8.02, 9.03, and the like. For comparison, the ratio of 8.0 is commonly used in the embodiments of the present invention.

In the above technical means, the content of the modifying element is preferably more than 0 and not more than 50 g/L. For convenience, the content of the modifying element is generally 25g/L in the embodiment of the invention.

In the above technical scheme, the ZSM-11 molecular sieve is preferably a hydrogen type molecular sieve.

In the above technical scheme, the mole ratio of silicon to aluminum of the molecular sieve is preferably SiO₂/Al₂O₃Is 20 to 200. For convenience of comparing, this bookThe specific embodiment of the invention generally adopts SiO₂/Al₂O₃Is 50.

In the technical scheme, the catalyst can achieve comparable technical effects with or without a molecular sieve binder. In the case of a catalyst comprising a molecular sieve binder, the skilled person can rationally select the usual binder without inventive step, for example, the molecular sieve binders that can be selected are pseudo-boehmite, alumina, silica, etc.

When the catalyst is passivated by the method comprising the following steps, the selectivity of monoethanolamine and diethanolamine in a product is obviously improved, and the catalyst can achieve the purpose of not containing triethanolamine:

contacting the catalyst with a passivation material, and passivating for 2-24 hours at 40-100 ℃, wherein the passivation material comprises ethylene oxide and ammonia water, and NH in the passivation material₃The molar ratio of the EO to the EO is 1 to 10.

The ammonia adopted in the reaction of the catalyst for increasing the production of the monoethanolamine and the diethanolamine is liquid ammonia, the catalyst is passivated by adopting ammonia water as a passivation raw material, and the selectivity of the catalyst is improved after the catalyst is passivated, but the liquid ammonia does not have the function.

In the passivation, the ammonia concentration in the ammonia water is preferably 20 to 95 w%, such as, but not limited to, 30 w%, 40 w%, 50 w%, 60 w%, 65 w%, 70 w%, 75 w%, 80 w%, 85 w%, 90 w%, 91 w%, 92 w%, 93 w%, 94 w%, 95 w%, and the like, and more preferably 60 to 95 w%.

However, in a comparable manner, the catalyst deactivation in the embodiment of the present invention is carried out by the following method:

heating the catalyst bed to 80 deg.C, and reacting according to NH₃Introducing ethylene oxide and ammonia water with the concentration of 90% into the EO (3) for catalyst passivation treatment, wherein the liquid phase volume space velocity of the ethylene oxide is 2.0 hours^-1The deactivation time was 24 hours. After the passivation is finished, the airspeed is 10.0 hours^-1Liquid ammonia was introduced into the reactor for 10 hours to displace the ammonia.

To solve the second technical problem, the technical solution of the present invention is as follows: the method for preparing the catalyst according to any one of the above technical problems, comprising:

mixing the molecular sieve with a compound solution of a modifying element;

drying;

and (4) roasting.

In the technical scheme, the drying temperature is preferably 60-150 ℃, and more preferably 80-120 ℃.

In the technical scheme, the drying time is preferably 4-24 hours, and more preferably 3-8 hours.

In the technical scheme, the roasting temperature is preferably 250-750 ℃, and more preferably 350-550 ℃.

In the above technical scheme, the roasting time is preferably 2-12 hours, and more preferably 2-8 hours.

In the technical scheme, the roasting atmosphere has no special requirement, and both oxidizing atmosphere and inert atmosphere can obtain comparable technical effects. Oxidizing atmosphere such as, but not limited to, optionally oxygen-containing atmosphere, preferably air atmosphere from the economical point of view; the inert gas atmosphere is selected from at least one of nitrogen or inert gas atmosphere, and the inert gas atmosphere can be nitrogen, helium, argon and the like. From an economic point of view, nitrogen is often used as the inert atmosphere. In a comparable manner, air atmospheres are used in embodiments of the invention.

In the above technical solutions, the compound of La element is not particularly limited, for example, but not limited to, lanthanum nitrate, lanthanum acetate, lanthanum oxalate, and the like.

In the above technical scheme, the compound of the element P is not particularly limited, such as but not limited to phosphoric acid, phosphorous acid, and the like.

In the above technical scheme, the compound of the K element is not particularly limited, and examples thereof include, but are not limited to, potassium hydroxide, potassium acetate, potassium nitrate, potassium carbonate, and the like.

In the above technical scheme, the compound of Na element is not particularly limited, such as but not limited to sodium hydroxide, sodium acetate, sodium nitrate, potassium carbonate, and the like.

In the above technical solution, the compound of Ni element is not particularly limited, for example, but not limited to, nickel nitrate, nickel acetate, and the like.

There is no particular limitation on the method for preparing the ZSM-11 molecular sieve, and those skilled in the art can make a reasonable choice without inventive effort. By way of example, the molecular sieves of embodiments of the invention can be prepared by a process comprising the steps of:

the ZSM-11 molecular sieve is preferably synthesized by the following method: a) dissolving an alkali source in water to obtain a solution I, adding an aluminum source into the solution I to obtain a solution II, adding an organic ammonium template into the solution II to obtain a solution III, and finally adding a silicon source, NaCl and an organic high polymer into the solution III to obtain a raw material mixture. Wherein the raw material mixture comprises the following components in molar ratio: SiO 2₂/Al₂O₃＝20～200，H₂O/SiO₂＝10～150，OH^-/SiO₂0.01 to 0.5 of a templating agent/SiO₂＝0.01～0.5，NaCl/SiO₂0.01 to 0.7 of organic high polymer/SiO₂0.0001 to 0.01. Wherein the organic ammonium is selected from at least one of tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium bromide, tetraethylammonium bromide or tetrapropylammonium bromide; the alkali source is at least one selected from lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide or cesium hydroxide; the silicon source is at least one of tetraethoxysilane, silica sol, water glass or white carbon black; the aluminum source is selected from at least one of aluminum oxide, sodium aluminate, sodium metaaluminate, aluminum hydroxide, aluminum sulfate or aluminum isopropoxide; the organic high polymer is selected from at least one of starch or polyethylene glycol; b) carrying out hydrothermal crystallization on the raw material mixture prepared in the step a) for 24-480 hours at the crystallization temperature of 60-200 ℃. And filtering, washing, drying and roasting the crystallized product to obtain the ZSM-5 molecular sieve. The preferred molar ratio of the components of the raw material mixture is SiO₂/Al₂O₃＝30～100，H₂O/SiO₂＝20～50，OH^-/SiO₂0.1 to 0.5 of a templating agent/SiO₂＝0.1～0.5，NaCl/SiO₂0.1 to 0.7 of organic high polymer/SiO₂0.001 to 0.01. The preferable crystallization temperature is 100-180 ℃, and the preferable crystallization time is 24-120 hours.

However, for the sake of comparison, the molecular sieve in the embodiment of the present invention is generally prepared by the following method:

a) firstly, NaOH is dissolved in water to obtain solution I, and NaAlO is added₂Adding the mixture into the solution I to obtain a solution II, adding TBABr into the solution II to obtain a solution III, and finally adding 40% of silica sol, NaCl and polyethylene glycol (10000) into the solution III to obtain a raw material mixture, wherein the molar ratio of the raw materials in the mixture is as follows: SiO 2₂/Al₂O₃＝50，H₂O/SiO₂＝50，NaCl/SiO₂＝0.68，NaOH/SiO₂＝0.15，TBABr/SiO₂0.40 polyethylene glycol (10000)/SiO₂0.02. b) Stirring the raw material mixture prepared in the step a) for 180 minutes, putting the mixture into a reaction kettle, and dynamically crystallizing the mixture at 170 ℃ (200 revolutions per minute) for 72 hours. The crystallized product is quenched, filtered and washed with water until the pH value is 7, and dried for 12 hours at 120 ℃ to prepare ZSM-11 molecular sieve raw powder

The obtained sodium-containing molecular sieve can be converted into a hydrogen-containing molecular sieve by a method well known to those skilled in the art, and the conversion is performed at the raw powder stage or after the molding, which is not particularly limited, and comparable technical effects can be obtained.

For example, in the embodiment of the present invention, the conversion of the molecular sieve into the hydrogen form molecular sieve is performed at the raw powder stage, which may specifically include the following steps: 0.1 to 1.0 mol.L is used^-1The solid-liquid ratio of the ammonium nitrate solution is 1: 10-1: 20, the solution is stirred for 1-5 hours at the temperature of 60-120 ℃, and then the solution is filtered and washed. The process is repeated for three times, the obtained sample is dried for 4-8 hours at the temperature of 60-150 ℃, and finally roasted for 2-12 hours at the temperature of 250-750 ℃ to obtain the hydrogen type ZSM-11 molecular sieve powder.

By way of comparison only, the steps for converting the molecular sieve to the hydrogen form of the molecular sieve in the embodiments of the present invention are as follows: use 0.2 mol. L^-1The ammonium nitrate solution has a solid-to-liquid ratio of 1:15, is heated at 90 ℃ and stirred for 2 hours, and then is filtered, washed. This procedure was repeated three times, and the resulting samples were dried at 120 ℃ for 6 hours, and finallyRoasting at 550 deg.c for 5 hr to obtain hydrogen type ZSM-11 molecular sieve powder.

Mixing hydrogen type ZSM-11 molecular sieve raw powder with boehmite, sesbania powder and water, wherein the weight part ratio of the raw materials is ZSM-11/Al₂O₃The powder/water of sesbania/sesbania is 55:19:1:25, extruded into strips, dried at 120 ℃ for 12 hours, and roasted at 550 ℃ for 5 hours to obtain the molecular sieve with the diameter of 1.0mm and the length of 3.0 mm.

To solve the third technical problem, the technical scheme of the invention is as follows:

use of a catalyst according to any of the preceding claims for the production of monoethanolamine and diethanolamine.

The technical key of the invention is the selection of the catalyst, and the specific process conditions of the specific application can be reasonably selected by a person skilled in the art without creative labor.

By way of example, the specific process conditions for the application of the catalyst of the invention may be:

EO and liquid NH in the presence of the catalyst₃The monoethanolamine and diethanolamine are generated by reaction.

In the technical scheme, the reaction temperature is preferably 60-100 DEG C

In the technical scheme, the reaction pressure is preferably 5.0-12.0 MPa. Unless otherwise specified, the pressures referred to herein are in terms of gauge pressure.

In the above-mentioned embodiment, NH is preferably used in terms of molar ratio₃/EO＝5～30。

In the technical scheme, the preferred volume airspeed of the liquid phase of the ethylene oxide is 0.2-2.2 hours^-1。

In comparison, the process conditions in the specific embodiment of the invention are as follows: the reaction temperature is 80 ℃, the reaction pressure is 6.0MPa, and the liquid NH is₃The molar ratio of the EO to the EO is 8, the volume space velocity of the EO liquid phase is 1.2 hours^-1。

By adopting the invention, the conversion rate of the Ethylene Oxide (EO) can reach 100%, and the selectivity of the monoethanolamine and the diethanolamine can reach 99.9%, thereby obtaining better technical effect.

Detailed Description

[ example 1 ]

1. Molecular sieve preparation

The prepared ZSM-11 molecular sieve raw powder is mixed by 0.2 mol.L^-1Soaking in ammonium nitrate solution at solid-to-liquid ratio of 1:15, heating at 90 deg.C, stirring for 2 hr, filtering, and washing. The process is repeated three times, the obtained sample is dried for 6 hours at 120 ℃, and finally roasted for 5 hours at 550 ℃ to obtain the hydrogen type ZSM-11 molecular sieve powder.

Mixing the synthesized ZSM-11 molecular sieve raw powder with boehmite, sesbania powder and water, wherein the weight part ratio of the raw materials is ZSM-11/Al₂O₃And (3) extruding and forming the powder/water of sesbania/sesbania powder/water of 55:19:1:25, drying the powder at 120 ℃ for 12 hours, and roasting the powder at 550 ℃ for 5 hours to obtain the formed hydrogen type molecular sieve with the diameter of 1.0mm and the length of 3.0 mm.

2. Catalyst preparation

1L of hydrogen type molecular sieve is taken and mixed with 0.6L of lanthanum nitrate aqueous solution (containing 25g of La), and the mixture is dried for 6 hours at 110 ℃ and roasted for 4 hours at 450 ℃.

The catalyst contained 25g/L of La.

3. Catalyst passivation

The catalyst was not passivated.

4. Catalyst evaluation

Catalyst evaluation conditions: the reaction temperature is 80 ℃, the reaction pressure is 6.0MPa, and the liquid NH is₃Molar ratio to EO of 8, EO liquid phase volume space velocityIs 1.2 hours^-1Then, catalyst evaluation was performed.

For comparison, the kinds and contents of the modifying elements, and the evaluation results of the catalyst are shown in Table 1.

[ example 2 ]

1. Molecular sieve preparation

2. Catalyst preparation

1L of hydrogen type molecular sieve was mixed with 0.6L of phosphoric acid aqueous solution (containing P25 g), dried at 110 ℃ for 6 hours, and calcined at 450 ℃ for 4 hours.

The catalyst contained P25 g/L.

3. Catalyst passivation

The catalyst was not passivated.

4. Catalyst evaluation

Catalyst evaluation conditions: the reaction temperature is 80 ℃, the reaction pressure is 6.0MPa, and the liquid NH is₃The molar ratio of the EO to the EO is 8, the volume space velocity of the EO liquid phase is 1.2 hours^-1Then, catalyst evaluation was performed.

[ example 3 ]

1. Molecular sieve preparation

2. Catalyst preparation

1L of hydrogen type molecular sieve is taken and mixed with 0.6L of potassium hydroxide solution (containing 25g of K), dried for 6 hours at 110 ℃ and roasted for 4 hours at 450 ℃.

The catalyst contained K25 g/L.

3. Catalyst passivation

The catalyst was not passivated.

4. Catalyst evaluation

[ example 4 ]

1. Molecular sieve preparation

Mixing the synthesized ZSM-11 molecular sieve raw powder with boehmite, sesbania powder and water, wherein the weight part ratio of the raw materials is ZSM-11/Al₂O₃Powder/water of 55:19:1:25, extruding into strips, drying at 120 deg.C for 12 hrAnd roasting at 550 ℃ for 5 hours to obtain the formed hydrogen type molecular sieve with the diameter of 1.0mm and the length of 3.0 mm.

2. Catalyst preparation

1L of hydrogen type molecular sieve was mixed with 0.6L of sodium hydroxide solution (containing 25g of Na), dried at 110 ℃ for 6 hours, and calcined at 450 ℃ for 4 hours.

The catalyst contained Na 25 g/L.

3. Catalyst passivation

The catalyst was not passivated.

4. Catalyst evaluation

[ example 5 ]

1. Molecular sieve preparation

2. Catalyst preparation

1L of hydrogen type molecular sieve was mixed with 0.6L of calcium nitrate solution (containing 25g of Ca), dried at 110 ℃ for 6 hours, and calcined at 450 ℃ for 4 hours.

The catalyst contained 25g/L Ca.

3. Catalyst passivation

The catalyst was not passivated.

4. Catalyst evaluation

[ example 6 ]

1. Molecular sieve preparation

The prepared ZSM-11 molecular sieve raw powder is mixed by 0.2 mol.L^-1Ammonium nitrate ofSoaking the solution at a solid-to-liquid ratio of 1:15, heating at 90 deg.C, stirring for 2 hr, filtering, and washing. The process is repeated three times, the obtained sample is dried for 6 hours at 120 ℃, and finally roasted for 5 hours at 550 ℃ to obtain the hydrogen type ZSM-11 molecular sieve powder.

2. Catalyst preparation

1L of hydrogen type molecular sieve is mixed with 0.6L of nickel nitrate solution (containing 25g of Ni), dried at 110 ℃ for 6 hours and roasted at 450 ℃ for 4 hours.

The catalyst contained Ni 25 g/L.

3. Catalyst passivation

The catalyst was not passivated.

4. Catalyst evaluation

[ example 7 ]

1. Molecular sieve preparation

a) Firstly, NaOH is dissolved in water to obtain solution I, and NaAlO is added₂Adding the mixture into the solution I to obtain a solution II, adding TBABr into the solution II to obtain a solution III, and finally adding 40% of silica sol, NaCl and polyethylene glycol (10000) into the solution III to obtain a raw material mixture, wherein the molar ratio of the raw materials in the mixture is as follows: SiO 2₂/Al₂O₃＝50，H₂O/SiO₂＝50，NaCl/SiO₂＝0.68，NaOH/SiO₂＝0.15，TBABr/SiO₂0.40 polyethylene glycol (10000)/SiO₂0.02. b) Stirring the raw material mixture prepared in the step a) for 180 minutes, putting the mixture into a reaction kettle, and carrying out dynamic (200 revolutions per minute) crystallization at 170 DEG CTake 72 hours. The crystallized product is quenched, filtered and washed with water until the pH value is 7, and dried for 12 hours at 120 ℃ to prepare ZSM-11 molecular sieve raw powder

2. Catalyst preparation

1L of hydrogen type molecular sieve is taken and mixed with 0.6L of mixed solution of lanthanum acetate and phosphoric acid (containing 20g of La and 5g of P), dried for 6 hours at 110 ℃, and roasted for 4 hours at 450 ℃.

The catalyst contains 20g/L of La and 5g/L of P.

3. Catalyst passivation

The catalyst was not passivated.

4. Catalyst evaluation

[ example 8 ]

1. Molecular sieve preparation

2. Catalyst preparation

1L of hydrogen type molecular sieve is taken and mixed with 0.6L of mixed solution of lanthanum oxalate and potassium acetate (containing 20g of La and 5g of K), dried for 6 hours at 110 ℃ and roasted for 4 hours at 450 ℃.

The catalyst contains 20g/L of La and 5g/L of K.

3. Catalyst passivation

The catalyst was not passivated.

4. Catalyst evaluation

[ example 9 ]

1. Molecular sieve preparation

a) Firstly, NaOH is dissolved in water to obtain solution I, and NaAlO is added₂Is added into the solution IAnd obtaining a solution II, adding TBABr into the solution II to obtain a solution III, and finally adding 40% of silica sol, NaCl and polyethylene glycol (10000) into the solution III to obtain a raw material mixture, wherein the molar ratio of the raw materials in the composition is as follows: SiO 2₂/Al₂O₃＝50，H₂O/SiO₂＝50，NaCl/SiO₂＝0.68，NaOH/SiO₂＝0.15，TBABr/SiO₂0.40 polyethylene glycol (10000)/SiO₂0.02. b) Stirring the raw material mixture prepared in the step a) for 180 minutes, putting the mixture into a reaction kettle, and dynamically crystallizing the mixture at 170 ℃ (200 revolutions per minute) for 72 hours. The crystallized product is quenched, filtered and washed with water until the pH value is 7, and dried for 12 hours at 120 ℃ to prepare ZSM-11 molecular sieve raw powder

2. Catalyst preparation

1L of hydrogen type molecular sieve is taken and mixed with 0.6L of mixed solution of lanthanum nitrate and sodium acetate (containing 20g of La and 5g of Na), dried for 6 hours at 110 ℃, and roasted for 4 hours at 450 ℃.

The catalyst contained 20g/L of La and 5g/L of Na.

3. Catalyst passivation

The catalyst was not passivated.

4. Catalyst evaluation

[ example 10 ]

1. Molecular sieve preparation

2. Catalyst preparation

1L of hydrogen type molecular sieve is taken and mixed with 0.6L of mixed solution of lanthanum nitrate and calcium nitrate (containing 20g of La and 5g of Ca), dried for 6 hours at 110 ℃ and roasted for 4 hours at 450 ℃.

The catalyst contains 20g/L of La and 5g/L of Ca.

3. Catalyst passivation

The catalyst was not passivated.

4. Catalyst evaluation

[ example 11 ]

1. Molecular sieve preparation

2. Catalyst preparation

1L of hydrogen type molecular sieve is taken and mixed with 0.6L of mixed solution of lanthanum nitrate and nickel acetate (containing 20g of La and 5g of Ni), dried for 6 hours at 110 ℃, and roasted for 4 hours at 450 ℃.

The catalyst contains 20g/L of La and 5g/L of Ni.

3. Catalyst passivation

The catalyst was not passivated.

4. Catalyst evaluation

[ example 12 ]

1. Molecular sieve preparation

Mixing the synthesized ZSM-11 molecular sieve raw powder with boehmite, sesbania powder and water, wherein the weight part ratio of the raw materials is ZSM-11/Al₂O₃Powder/water of 55:19:1:25, extruding into strips, drying at 120 deg.C for 12 hr, baking at 550 deg.C for 5 hr to obtain powder with diameter of 1.0mm and length of 1.0mm3.0mm of formed hydrogen type molecular sieve.

2. Catalyst preparation

1L of hydrogen type molecular sieve is taken and mixed with 0.6L of mixed solution (containing 20g of La, 2.5g of P and 2.5g of K) of lanthanum nitrate, phosphoric acid and potassium carbonate, dried for 6 hours at 110 ℃ and roasted for 4 hours at 450 ℃.

The catalyst contains 20g/L of La, 2.5g/L of P and 2.5g/L of K.

3. Catalyst passivation

The catalyst was not passivated.

4. Catalyst evaluation

[ example 13 ]

1. Molecular sieve preparation

2. Catalyst preparation

1L of hydrogen type molecular sieve is taken and mixed with 0.6L of mixed solution of lanthanum nitrate, phosphoric acid and calcium carbonate (containing 20g of La, 2.5g of P and 2.5g of Ca), dried for 6 hours at 110 ℃ and roasted for 4 hours at 450 ℃.

The catalyst contained 20g/L of La, 2.5g/L of P and 2.5g/L of Ca.

3. Catalyst passivation

The catalyst was not passivated.

4. Catalyst evaluation

[ example 14 ]

1. Molecular sieve preparation

2. Catalyst preparation

1L of hydrogen type molecular sieve is taken and mixed with 0.6L of mixed solution of lanthanum nitrate, phosphoric acid and nickel nitrate (containing 20g of La, 2.5g of P and 2.5g of Ni), dried at 110 ℃ for 6 hours and roasted at 450 ℃ for 4 hours.

The catalyst contains 20g/L of La, 2.5g/L of P and 2.5g/L of Ni.

3. Catalyst passivation

The catalyst was not passivated.

4. Catalyst evaluation

[ example 15 ]

1. Molecular sieve preparation

2. Catalyst preparation

1L of hydrogen type molecular sieve is taken and mixed with 0.6L of mixed solution of lanthanum nitrate, potassium carbonate and nickel nitrate (containing 20g of La, 2.5g of K and 2.5g of Ni), dried at 110 ℃ for 6 hours and roasted at 450 ℃ for 4 hours.

The catalyst contains 20g/L of La, 2.5g/L of K and 2.5g/L of Ni.

3. Catalyst passivation

The catalyst was not passivated.

4. Catalyst evaluation

[ example 16 ]

1. Molecular sieve preparation

a) Firstly, NaOH is dissolved in water to obtain solution I, and NaAlO is added₂Adding into solution I to obtain solution II, adding TBABr into solution II to obtain solution IIIAnd adding 40% silica sol, NaCl and polyethylene glycol (10000) into the solution III to obtain a raw material mixture, wherein the molar ratio of the raw materials in the mixture is as follows: SiO 2₂/Al₂O₃＝50，H₂O/SiO₂＝50，NaCl/SiO₂＝0.68，NaOH/SiO₂＝0.15，TBABr/SiO₂0.40 polyethylene glycol (10000)/SiO₂0.02. b) Stirring the raw material mixture prepared in the step a) for 180 minutes, putting the mixture into a reaction kettle, and dynamically crystallizing the mixture at 170 ℃ (200 revolutions per minute) for 72 hours. The crystallized product is quenched, filtered and washed with water until the pH value is 7, and dried for 12 hours at 120 ℃ to prepare ZSM-11 molecular sieve raw powder

2. Catalyst preparation

1L of hydrogen type molecular sieve was taken, mixed with 0.6L of a mixed solution of lanthanum nitrate, sodium hydroxide and calcium nitrate (containing 20g of La, 2.5g of Na and 2.5g of Ca), dried at 110 ℃ for 6 hours, and calcined at 450 ℃ for 4 hours.

The catalyst contained 20g/L of La, 2.5g/L of Na and 2.5g/L of Ca.

3. Catalyst passivation

The catalyst was not passivated.

4. Catalyst evaluation

[ example 1' ]

1. Molecular sieve preparation

2. Catalyst preparation

The catalyst contained 25g/L of La.

3. Catalyst passivation

Heating the catalyst bed to 80 deg.C, and reacting according to NH₃Introducing ethylene oxide and 90% ammonia water in the proportion of 3/EO to passivate the catalystThe liquid phase volume space velocity of ethane was 2.0 hours^-1The deactivation time was 24 hours. After the passivation is finished, the volume airspeed is 10.0 hours^-1Liquid ammonia was introduced into the reactor for 10 hours to displace the ammonia.

4. Catalyst evaluation

[ example 2' ]

1. Molecular sieve preparation

Mixing the synthesized ZSM-11 molecular sieve raw powder with boehmite, sesbania powder and water, wherein the weight part ratio of the raw materials is ZSM-11/Al₂O₃The powder/water of sesbania sessilifolia (55: 19:1: 25) is extruded into strips, dried at 120 ℃ for 12 hours and baked at 550 ℃ for 5 hours to obtain the powder with the diameter of 1.0mm and the length of 1.0mmIs a 3.0mm molded hydrogen molecular sieve.

2. Catalyst preparation

The catalyst contained P25 g/L.

3. Catalyst passivation

Heating the catalyst bed to 80 deg.C, and reacting according to NH₃Introducing ethylene oxide and ammonia water with the concentration of 90% into the EO (3) for catalyst passivation treatment, wherein the liquid phase volume space velocity of the ethylene oxide is 2.0 hours^-1The deactivation time was 24 hours. After the passivation is finished, the volume airspeed is 10.0 hours^-1Liquid ammonia was introduced into the reactor for 10 hours to displace the ammonia.

4. Catalyst evaluation

[ example 3' ]

1. Molecular sieve preparation

The prepared ZSM-11 molecular sieveThe raw powder is added in an amount of 0.2 mol.L^-1Soaking in ammonium nitrate solution at solid-to-liquid ratio of 1:15, heating at 90 deg.C, stirring for 2 hr, filtering, and washing. The process is repeated three times, the obtained sample is dried for 6 hours at 120 ℃, and finally roasted for 5 hours at 550 ℃ to obtain the hydrogen type ZSM-11 molecular sieve powder.

2. Catalyst preparation

The catalyst contained K25 g/L.

3. Catalyst passivation

4. Catalyst evaluation

[ example 4' ]

1. Molecular sieve preparation

a) Firstly, NaOH is dissolved in water to obtain solution I, and NaAlO is added₂Adding into solution I to obtain solution II, adding TBABr into solution II to obtain solution III, and adding 40% silica sol, NaCl, and polyethylene glycol (10000) into solution III to obtain raw material mixtureThe molar ratio of the raw materials in the composition is as follows: SiO 2₂/Al₂O₃＝50，H₂O/SiO₂＝50，NaCl/SiO₂＝0.68，NaOH/SiO₂＝0.15，TBABr/SiO₂0.40 polyethylene glycol (10000)/SiO₂0.02. b) Stirring the raw material mixture prepared in the step a) for 180 minutes, putting the mixture into a reaction kettle, and dynamically crystallizing the mixture at 170 ℃ (200 revolutions per minute) for 72 hours. The crystallized product is quenched, filtered and washed with water until the pH value is 7, and dried for 12 hours at 120 ℃ to prepare ZSM-11 molecular sieve raw powder

2. Catalyst preparation

The catalyst contained Na 25 g/L.

3. Catalyst passivation

4. Catalyst evaluation

Catalyst evaluation conditions: the reaction temperature is 80 ℃, the reaction pressure is 6.0MPa, and the liquid NH is₃The molar ratio of the EO to the EO is 8, the volume space velocity of the EO liquid phase is 12 hours^-1Then, catalyst evaluation was performed.

[ example 5' ]

1. Molecular sieve preparation

2. Catalyst preparation

The catalyst contained 25g/L Ca.

3. Catalyst passivation

Heating catalysisThe agent bed reaches 80 ℃, and after the temperature is constant, the agent bed is treated according to NH₃Introducing ethylene oxide and ammonia water with the concentration of 90% into the EO (3) for catalyst passivation treatment, wherein the liquid phase volume space velocity of the ethylene oxide is 2.0 hours^-1The deactivation time was 24 hours. After the passivation is finished, the volume airspeed is 10.0 hours^-1Liquid ammonia was introduced into the reactor for 10 hours to displace the ammonia.

4. Catalyst evaluation

[ example 6' ]

1. Molecular sieve preparation

Mixing the synthesized ZSM-11 molecular sieve raw powder with boehmite, sesbania powder and water, wherein the weight part ratio of each raw material isZSM-11/Al₂O₃And (3) extruding and forming the powder/water of sesbania/sesbania powder/water of 55:19:1:25, drying the powder at 120 ℃ for 12 hours, and roasting the powder at 550 ℃ for 5 hours to obtain the formed hydrogen type molecular sieve with the diameter of 1.0mm and the length of 3.0 mm.

2. Catalyst preparation

The catalyst contained Ni 25 g/L.

3. Catalyst passivation

4. Catalyst evaluation

[ example 7' ]

1. Molecular sieve preparation

a) Firstly, NaOH is dissolved in water to obtain solution I, and NaAlO is added₂Adding the mixture into the solution I to obtain a solution II, adding TBABr into the solution II to obtain a solution III, and finally adding 40% of silica sol, NaCl and polyethylene glycol (10000) into the solution III to obtain a raw material mixture, wherein the molar ratio of the raw materials in the mixture is as follows: SiO 2₂/Al₂O₃＝50，H₂O/SiO₂＝50，NaCl/SiO₂＝0.68，NaOH/SiO₂＝0.15，TBABr/SiO₂0.40 polyethylene glycol (10000)/SiO₂0.02. b) Stirring the raw material mixture prepared in the step a) for 180 minutes, putting the mixture into a reaction kettle, and dynamically crystallizing the mixture at 170 ℃ (200 revolutions per minute) for 72 hours. Crystallized productQuenching, filtering, washing with water to pH 7, oven drying at 120 deg.C for 12 hr to obtain ZSM-11 molecular sieve raw powder

2. Catalyst preparation

The catalyst contains 20g/L of La and 5g/L of P.

3. Catalyst passivation

4. Catalyst evaluation

[ example 8' ]

1. Molecular sieve preparation

a) Dissolving NaOH in water to obtain solution I, dissolving NaOH in water to obtain solution INaAlO₂Adding the mixture into the solution I to obtain a solution II, adding TBABr into the solution II to obtain a solution III, and finally adding 40% of silica sol, NaCl and polyethylene glycol (10000) into the solution III to obtain a raw material mixture, wherein the molar ratio of the raw materials in the mixture is as follows: SiO 2₂/Al₂O₃＝50，H₂O/SiO₂＝50，NaCl/SiO₂＝0.68，NaOH/SiO₂＝0.15，TBABr/SiO₂0.40 polyethylene glycol (10000)/SiO₂0.02. b) Stirring the raw material mixture prepared in the step a) for 180 minutes, putting the mixture into a reaction kettle, and dynamically crystallizing the mixture at 170 ℃ (200 revolutions per minute) for 72 hours. The crystallized product is quenched, filtered and washed with water until the pH value is 7, and dried for 12 hours at 120 ℃ to prepare ZSM-11 molecular sieve raw powder

2. Catalyst preparation

The catalyst contains 20g/L of La and 5g/L of K.

3. Catalyst passivation

Heating the catalyst bed to 80 deg.C, and reacting according to NH₃Introducing ethylene oxide and ammonia water with the concentration of 90% into the EO (3) for catalyst passivation treatment, wherein the liquid phase volume space velocity of the ethylene oxide is 2.0 hours^-1The deactivation time was 24 hours. After the passivation is finished, the volume airspeed is 10.0 hours^-1Liquid ammonia is introduced into the reactor for 10 hours to replace ammoniaAnd (3) water.

4. Catalyst evaluation

[ example 9' ]

1. Molecular sieve preparation

2. Catalyst preparation

The catalyst contained 20g/L of La and 5g/L of Na.

3. Catalyst passivation

4. Catalyst evaluation

[ example 10' ]

1. Molecular sieve preparation

The prepared ZSM-11 molecular sieve raw powder is mixed by 0.2 mol.L^-1Soaking in ammonium nitrate solution at solid-to-liquid ratio of 1:15, heating at 90 deg.C, stirring for 2 hr, filtering, and washing. The process isThe process is repeated three times, the obtained sample is dried for 6 hours at 120 ℃, and finally roasted for 5 hours at 550 ℃ to obtain the hydrogen type ZSM-11 molecular sieve powder.

2. Catalyst preparation

The catalyst contains 20g/L of La and 5g/L of Ca.

3. Catalyst passivation

4. Catalyst evaluation

[ example 11' ]

1. Molecular sieve preparation

2. Catalyst preparation

The catalyst contains 20g/L of La and 5g/L of Ni.

3. Catalyst passivation

4. Catalyst evaluation

[ example 12' ]

1. Molecular sieve preparation

2. Catalyst preparation

The catalyst contains 20g/L of La, 2.5g/L of P and 2.5g/L of K.

3. Catalyst passivation

4. Catalyst evaluation

[ example 13' ]

1. Molecular sieve preparation

Mixing the synthesized ZSM-11 molecular sieve raw powder with boehmite, sesbania powder and waterThe weight portion ratio of ZSM-11/Al₂O₃And (3) extruding and forming the powder/water of sesbania/sesbania powder/water of 55:19:1:25, drying the powder at 120 ℃ for 12 hours, and roasting the powder at 550 ℃ for 5 hours to obtain the formed hydrogen type molecular sieve with the diameter of 1.0mm and the length of 3.0 mm.

2. Catalyst preparation

The catalyst contained 20g/L of La, 2.5g/L of P and 2.5g/L of Ca.

3. Catalyst passivation

4. Catalyst evaluation

[ example 14' ]

1. Molecular sieve preparation

a) Firstly, NaOH is dissolved in water to obtain solution I, and NaAlO is added₂Adding the mixture into the solution I to obtain a solution II, adding TBABr into the solution II to obtain a solution III, and finally adding 40% of silica sol, NaCl and polyethylene glycol (10000) into the solution III to obtain a raw material mixture, wherein the molar ratio of the raw materials in the mixture is as follows: SiO 2₂/Al₂O₃＝50，H₂O/SiO₂＝50，NaCl/SiO₂＝0.68，NaOH/SiO₂＝0.15，TBABr/SiO₂0.40 polyethylene glycol (10000)/SiO₂0.02. b) Stirring the raw material mixture prepared in the step a)Stirring for 180 minutes, placing into a reaction kettle, and dynamically crystallizing at 170 ℃ (200 revolutions per minute) for 72 hours. The crystallized product is quenched, filtered and washed with water until the pH value is 7, and dried for 12 hours at 120 ℃ to prepare ZSM-11 molecular sieve raw powder

2. Catalyst preparation

The catalyst contains 20g/L of La, 2.5g/L of P and 2.5g/L of Ni.

3. Catalyst passivation

4. Catalyst evaluation

[ example 15' ]

1. Molecular sieve preparation

2. Catalyst preparation

The catalyst contains 20g/L of La, 2.5g/L of K and 2.5g/L of Ni.

3. Catalyst passivation

Heating the catalyst bed to 80 deg.C, and reacting according to NH₃Introducing ethylene oxide and 90% ammonia water in the proportion of 3/EO to passivate the catalystHas a liquid phase volume space velocity of 2.0 hours^-1The deactivation time was 24 hours. After the passivation is finished, the volume airspeed is 10.0 hours^-1Liquid ammonia was introduced into the reactor for 10 hours to displace the ammonia.

4. Catalyst evaluation

[ example 16' ]

1. Molecular sieve preparation

Mixing the synthesized ZSM-11 molecular sieve raw powder with boehmite, sesbania powder and water, wherein the weight part ratio of the raw materials is ZSM-11/Al₂O₃Tabanian powder/water 55:19:1:25, extrusion molding, oven drying at 120 deg.C for 12 hr, baking at 550 deg.C for 5 hr to obtain powder with diameter of 1.0mm and length of 3.0mm of formed hydrogen type molecular sieve.

2. Catalyst preparation

The catalyst contained 20g/L of La, 2.5g/L of Na and 2.5g/L of Ca.

3. Catalyst passivation

4. Catalyst evaluation

Catalyst evaluation conditions: reaction temperature 80 deg.C, reaction pressure 6.0Mpa, liquid NH₃The molar ratio of the EO to the EO is 8, the volume space velocity of the EO liquid phase is 1.2 hours^-1Then, catalyst evaluation was performed.

[ example 17' ]

1. Molecular sieve preparation

a) Firstly, NaOH is dissolved in water to obtain solution I, and NaAlO is added₂Adding the mixture into the solution I to obtain a solution II, adding TBABr into the solution II to obtain a solution III, and finally adding 40% of silica sol, NaCl and polyethylene glycol (10000) into the solution III to obtain a raw material mixture, wherein the molar ratio of the raw materials in the mixture is as follows: SiO 2₂/Al₂O₃＝50，H₂O/SiO₂＝50，NaCl/SiO₂＝0.68，NaOH/SiO₂＝0.15，TBABr/SiO₂0.40 polyethylene glycol (10000)/SiO₂0.02. b) Stirring the raw material mixture prepared in the step a) for 180 minutes, putting the mixture into a reaction kettle, and dynamically crystallizing the mixture at 170 ℃ (200 revolutions per minute) for 72 hours. The crystallized product is quenched, filtered and washed until the pH value is 7, and dried for 12 hours at 120 ℃ to prepare ZSM-11 molecular sieve raw powder

2. Catalyst preparation

The catalyst contained 20g/L of La, 2.5g/L of Na and 2.5g/L of Ca.

3. Catalyst passivation

Heating the catalyst bed to 80 deg.C, and reacting according to NH₃Introducing ethylene oxide and liquid ammonia in the proportion of EO (3) for catalyst passivation treatment, wherein the liquid phase volume space velocity of the ethylene oxide is 2.0 hours^-1The deactivation time was 24 hours.

4. Catalyst evaluation

TABLE 1

Note: example 17 'is the same as example 16' except that the aqueous ammonia in the passivation mass is replaced by liquid ammonia.

Claims

1. The catalyst is a passivated catalyst obtained by contacting a fresh catalyst for producing the monoethanolamine and the diethanolamine with a passivated material to perform a catalyst passivation reaction, and the passivation conditions are as follows: passivating for 2-24 hours at 40-100 ℃, wherein the passivating material comprises ethylene oxide and ammonia water, and NH is contained in the passivating material₃The molar ratio of the ethylene oxide to the ethylene oxide is 1-10; the ammonia concentration of the ammonia water is 20-95 w%; the fresh catalyst for producing the monoethanolamine and the diethanolamine comprises a ZSM-11 molecular sieve and molecular sieve modification elements, wherein the modification elements comprise La, Ni and P.

2. The catalyst of claim 1, wherein the content of the modifying element in the fresh catalyst for producing monoethanolamine and diethanolamine is more than 0 and less than 50 g/L.

3. The catalyst of claim 1, wherein the ZSM-11 sieve in the fresh monoethanolamine and diethanolamine production catalyst is a hydrogen type molecular sieve.

4. The catalyst of claim 1, wherein the fresh monoethanolamine and diethanolamine production catalyst contains the ZSM-11 molecular sieve having a silica to alumina molar ratio SiO₂/Al₂O₃Is 20 to 200.

5. The catalyst of claim 1, wherein the fresh monoethanolamine and diethanolamine producing catalyst is with or without a molecular sieve binder.

6. The catalyst according to claim 1, wherein the concentration of ammonia in the aqueous ammonia is 60 to 95 w% in the passivation process.

7. A method of preparing the catalyst of claim 1, comprising:

mixing the ZSM-11 molecular sieve with a compound solution of a modifying element;

drying;

roasting;

and (5) passivating.

8. The method according to claim 7, wherein the drying temperature is 60 to 150 ℃.

9. The method as claimed in claim 7, wherein the calcination temperature is 250 to 750 ℃.

10. The method as claimed in claim 7, wherein the calcination is carried out for 2 to 12 hours.

11. Use of the catalyst of any one of claims 1 to 6 in the production of monoethanolamine and diethanolamine.

12. Use of a catalyst according to claim 11, wherein ethylene oxide is reacted with liquid ammonia in the presence of a catalyst according to any one of claims 1 to 6 to produce monoethanolamine and diethanolamine.

13. The use of the catalyst according to claim 11, wherein the process conditions for producing monoethanolamine and diethanolamine are as follows: the reaction temperature is 60-100 ℃, the reaction pressure is 5.0-12.0 MPa, the molar ratio of liquid ammonia to ethylene oxide is 5-30, and the liquid phase volume airspeed of ethylene oxide is 0.2-2.2 hours^-1。