CN114247470A - Preparation method of catalyst and synthesis method of monoisopropanolamine - Google Patents
Preparation method of catalyst and synthesis method of monoisopropanolamine Download PDFInfo
- Publication number
- CN114247470A CN114247470A CN202111674635.6A CN202111674635A CN114247470A CN 114247470 A CN114247470 A CN 114247470A CN 202111674635 A CN202111674635 A CN 202111674635A CN 114247470 A CN114247470 A CN 114247470A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- temperature
- isopropanolamine
- liquid ammonia
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 88
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 238000001308 synthesis method Methods 0.000 title claims description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 53
- 229940102253 isopropanolamine Drugs 0.000 claims abstract description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000001914 filtration Methods 0.000 claims abstract description 28
- 159000000007 calcium salts Chemical class 0.000 claims abstract description 25
- 238000001035 drying Methods 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 15
- 238000003756 stirring Methods 0.000 claims abstract description 11
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 10
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 10
- 229910052680 mordenite Inorganic materials 0.000 claims abstract description 9
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 6
- 238000005406 washing Methods 0.000 claims abstract description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 54
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 36
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 36
- 238000010438 heat treatment Methods 0.000 claims description 24
- 238000001816 cooling Methods 0.000 claims description 22
- 229910052757 nitrogen Inorganic materials 0.000 claims description 21
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical group [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 16
- 238000004519 manufacturing process Methods 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 claims description 5
- 235000011092 calcium acetate Nutrition 0.000 claims description 5
- 239000001639 calcium acetate Substances 0.000 claims description 5
- 229960005147 calcium acetate Drugs 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 238000005470 impregnation Methods 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 239000000706 filtrate Substances 0.000 claims description 2
- LVTYICIALWPMFW-UHFFFAOYSA-N diisopropanolamine Chemical compound CC(O)CNCC(C)O LVTYICIALWPMFW-UHFFFAOYSA-N 0.000 abstract description 38
- 229940043276 diisopropanolamine Drugs 0.000 abstract description 38
- SLINHMUFWFWBMU-UHFFFAOYSA-N Triisopropanolamine Chemical compound CC(O)CN(CC(C)O)CC(C)O SLINHMUFWFWBMU-UHFFFAOYSA-N 0.000 abstract description 24
- 230000000694 effects Effects 0.000 abstract description 5
- 238000002791 soaking Methods 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 87
- 238000004321 preservation Methods 0.000 description 20
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 7
- 238000011084 recovery Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 5
- 238000005265 energy consumption Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 229910001424 calcium ion Inorganic materials 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 2
- 235000011130 ammonium sulphate Nutrition 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- -1 diisopropyl alcohol Chemical compound 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000005555 metalworking Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 231100000957 no side effect Toxicity 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/18—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/04—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reaction of ammonia or amines with olefin oxides or halohydrins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a preparation method of a catalyst, which is used for synthesizing isopropanolamine, and the preparation method of the catalyst comprises the following steps: (1) dissolving water-soluble calcium salt in water to prepare calcium salt water solution; (2) adding hydrogen-type mordenite (H-MOR) into calcium salt water solution, soaking in excess, stirring at constant temperature, filtering, washing, and drying; (3) and (3) after repeating the step (2) for a plurality of times, roasting the dried sample to obtain the catalyst. The application also discloses a method for synthesizing monoisopropanolamine by using the catalyst. The catalyst prepared by the method can be used as a catalyst for isopropanolamine synthesis, has excellent activity and selectivity in a reaction process, can effectively improve the proportion of monoisopropanolamine in a synthetic product, avoids generating triisopropanolamine, and reduces the proportion of diisopropanolamine.
Description
Technical Field
The invention relates to a preparation method of a catalyst and a method for synthesizing isopropanolamine by using the catalyst.
Background
Monoisopropanolamine (MIPA) is an alcamines compound with amino and alcoholic hydroxyl, and has the comprehensive performance of amine and alcohol. Because the isopropanolamine product has the advantages of low toxicity, safety, no side effect, environmental protection and the like, the isopropanolamine product is widely applied to the fields of surfactants, medical and pesticide intermediates, metal working fluids, fiber processing aids, paints, coatings, personal care products, titanium dioxide and the like, and has wide market prospect.
At present, most of industrial methods for producing isopropanolamine are to synthesize isopropanolamine series mixtures by using liquid ammonia and propylene oxide as raw materials and water as a catalyst, and then gradually separate three products, namely, Monoisopropanolamine (MIPA), Diisopropanolamine (DIPA) and Triisopropanolamine (TIPA). However, the monoisopropanolamine in the synthetic product of the process is low in proportion, a large amount of diisopropanolamine and triisopropanolamine can be produced, the production cost is increased, and the quality of the separated triisopropanolamine is poor, so that the market requirement cannot be met.
The patent CN110327967A provides a novel catalyst, ammonium sulfate is used for modifying the HZSM-5 molecular sieve, and the synthesized catalyst can be used for synthesizing isopropanolamine. The product produced by the catalyst mainly contains monoisopropanolamine, but still contains a certain amount of triisopropanolamine. The process adopts high ammonia-alkane ratio, the recovery amount of liquid ammonia is large, the requirement on equipment is high, and ammonium sulfate is easy to decompose and gasify in the roasting process of the catalyst and is difficult to prepare.
The patent CN112076780A uses Pd/Au/La-ZSM as a catalyst, and adopts liquid ammonia and propylene oxide to synthesize isopropanolamine. The product produced by the application mainly contains triisopropanolamine, contains a small amount of monoisopropanolamine, and is expensive due to the adoption of noble metal.
Although the prior art can produce isopropanolamine mixed products with monoisopropanolamine as a main component, the isopropanolamine mixed products still contain trace amounts of diisopropanolamine and triisopropanolamine when being separated, and a step-by-step separation method is needed to separate the diisopropanolamine and the triisopropanolamine in the isopropanolamine mixed products to obtain high-purity monoisopropanolamine products, so the production cost is extremely high,
because isopropanolamine series products belong to heat-sensitive substances, the chromaticity of the products is easily increased and impurities are increased due to overhigh temperature. The boiling point of triisopropanolamine is 305 ℃, the rectification temperature is higher, and triisopropanolamine products obtained by rectification have high chroma and low purity, thus the requirements of markets cannot be met.
Disclosure of Invention
In order to solve the above problems, the present invention firstly provides a method for preparing a catalyst, which is used for synthesizing isopropanolamine, the method for preparing the catalyst comprises the following steps:
(1) dissolving water-soluble calcium salt in water to prepare calcium salt water solution;
(2) adding hydrogen-type mordenite (H-MOR) into calcium salt water solution, soaking in excess, stirring at constant temperature, filtering, washing, and drying;
(3) and (3) after repeating the step (2) for a plurality of times, roasting the dried sample to obtain the catalyst. Specifically, the water-soluble calcium salt is calcium nitrate or calcium acetate.
In the catalyst, active component Ca ions are introduced into hydrogen mordenite through ion exchange to form a new catalyst, and experiments show that only Ca ions are introduced into hydrogen mordenite to effectively improve the reaction selectivity, so that when ammonia reacts with propylene oxide, isopropanolamine is more likely to be generated, a small amount of diisopropanolamine is only generated, and triisopropanolamine is not generated any more.
The catalyst prepared by the method can be used as a catalyst for isopropanolamine synthesis, has excellent activity and selectivity in a reaction process, can effectively improve the proportion of monoisopropanolamine in a synthetic product, avoids generating triisopropanolamine, and reduces the proportion of diisopropanolamine. Because triisopropanolamine is not used, the separation steps of all components in the product are simplified, the production efficiency is improved, and the production cost is reduced. And the produced diisopropanolamine does not contain triisopropanolamine, so that the purity of the diisopropanolamine product is improved.
In addition, when the catalyst prepared by the method is used for producing isopropanolamine, no supplementary water is needed as a solvent or the catalyst, so that the recovery of water is avoided, the energy consumption of products is reduced, the side reaction of propylene oxide and water is reduced, and the utilization rate of raw materials is improved.
The invention adopts low ammonia-alkane ratio and non-water system, reduces the recovery amount of liquid ammonia, avoids the recovery of water, reduces energy consumption and working hours, and also reduces the side reaction of propylene oxide and water.
Meanwhile, the synthesis proportion of the three isopropanolamine products in the reaction meets the demand of the existing market, the inventory of the products is reduced, and the storage cost and the requirement are reduced.
Specifically, the concentration of the calcium salt aqueous solution is 0.1-0.3 mol/L. At this concentration, calcium ions in the aqueous calcium salt solution can be smoothly loaded on the hydrogen mordenite. Tests show that when the concentration of the calcium salt aqueous solution is too low, the calcium salt aqueous solution cannot be uniformly distributed on the hydrogen-type mordenite, and when the concentration of the calcium salt aqueous solution is too high, raw materials are wasted.
Furthermore, in order to enable the calcium salt to be smoothly loaded on the hydrogen-type mordenite, the temperature during constant-temperature stirring is 30-60 ℃, and the stirring time is 4-8 hours. Too high a temperature leads to an increased solubility of the calcium salt in water, resulting in a lower loading and an uneven distribution of the calcium salt. Too low a temperature is detrimental to the effective loading of the calcium salt on the hydrogen mordenite.
Specifically, during drying, the drying temperature is 100-120 ℃, and the drying time is 12-24 hours each time.
The drying is mainly used for drying moisture, and the drying temperature of 100-120 ℃ is favorable for quickly and efficiently achieving the purpose. The drying time is too long when the temperature is low, and the energy consumption is wasted when the temperature is too high.
Specifically, the roasting temperature is 400-500 ℃, and the roasting time is 2-5 h.
The calcination of the catalyst is mainly to convert calcium salts into calcium oxide and to make the catalyst have a suitable pore structure, so that diisopropanolamine and triisopropanolamine are difficult or impossible to pass through the pore structure. This effect cannot be obtained unless the temperature and time are within the ranges.
Secondly, the application also discloses a synthesis method of the monoisopropanolamine, which comprises the following steps:
(1) adding a catalyst into a high-pressure kettle, replacing the catalyst with nitrogen, introducing epoxypropane and liquid ammonia, heating to a set temperature, preserving heat, and reacting; the catalyst is prepared by any one of the preparation methods;
(2) after the reaction is finished, cooling, denitrifying, filtering, recovering the catalyst, and rectifying the filtrate under reduced pressure to obtain the isopropanolamine.
No water is added in the synthesis process. In the synthesis method, the reactants including the catalyst and epoxypropane, liquid ammonia and the like are all free of moisture.
In the synthesis method, the catalyst has excellent activity and selectivity, the proportion of monoisopropanolamine in a synthesized product can be effectively improved, triisopropanolamine is prevented from being generated, and the proportion of diisopropanolamine is reduced. Because triisopropanolamine is not used, the separation steps of all components in the product are simplified, the production efficiency is improved, and the production cost is reduced. And the produced diisopropanolamine does not contain triisopropanolamine, so that the purity of the diisopropanolamine product is improved. In the synthesis method, the catalyst and all the raw materials do not contain moisture, and no moisture is needed to be added, so that the recovery of water is avoided, the energy consumption of the product is reduced, the side reaction of the propylene oxide and the water is reduced, and the utilization rate of the raw materials is improved. In the synthesis method, the ammonia-alkane ratio is effectively reduced, and the recovery amount of liquid ammonia is reduced.
Specifically, in order to ensure that the reaction is smoothly carried out, in the step (1), the adding amount of the catalyst is 6-10% of the total mass of the epoxypropane and the liquid ammonia, and the molar ratio of the liquid ammonia to the epoxypropane is 8-12: 1.
The catalyst is used for controlling the proportion, so that the smooth reaction can be ensured, and the monoisopropanolamine can be generated to the maximum extent under the condition of low ammonia-alkane ratio. When the using amount of the catalyst is small, the catalytic effect is poor, and the conversion rate of the propylene oxide is low; too large an amount of catalyst affects the stirring efficiency and increases the recovery throughput of the catalyst.
Further, the set temperature is 40-60 ℃, and the reaction time is 2-4 h. If the temperature is too low, the reaction is incomplete, and the conversion rate of the propylene oxide is low; a too high temperature leads to an increase in the proportion of diisopropyl alcohol. The reaction is incomplete due to too short reaction time, the conversion rate and the yield are not greatly influenced due to too long reaction time, and the working hours and the energy consumption are increased.
Detailed Description
So that the technical features and contents of the present invention can be understood in detail, the present invention will be further described with reference to specific embodiments.
Examples 1-3 below are for the preparation of catalysts.
Example 1
(1) Calcium acetate is prepared into a calcium acetate water solution with the concentration of 0.1 mol/L.
(2) Adding 50g H-MOR into a flask, adding 500ml of 0.1mol/L calcium acetate aqueous solution for excessive impregnation to ensure that calcium salt is uniformly distributed on the H-MOR, magnetically stirring for 8H in a constant-temperature water bath kettle at 30 ℃, filtering, washing, and drying the sample in a constant-temperature drying oven at 100 ℃ for 24H.
(3) After repeating step (2) twice, the dried sample was calcined at 500 ℃ for 2h to obtain a sample labeled C1.
Example 2
(1) Calcium nitrate is prepared into a calcium nitrate water solution with the concentration of 0.2 mol/L.
(2) Weighing 50g H-MOR, adding into a four-neck flask, adding 500ml of 0.2mol/L calcium nitrate water solution for excessive impregnation to ensure that the calcium salt is uniformly distributed on the H-MOR, magnetically stirring for 6H in a constant-temperature water bath kettle at 45 ℃, filtering, washing, and drying the sample in a constant-temperature drying oven at 110 ℃ for 18H.
(3) After repeating the step (2) twice, the dried sample was calcined at 450 ℃ for 4h, and the obtained sample was labeled as C2.
Example 3
(1) Calcium nitrate is prepared into a calcium nitrate water solution with the concentration of 0.3 mol/L.
(2) Weighing 50g H-MOR, adding into a four-neck flask, adding 500ml of 0.3mol/L calcium nitrate water solution for excessive impregnation to ensure that the calcium salt is uniformly distributed on the H-MOR, magnetically stirring for 4H in a constant-temperature water bath kettle at 30 ℃, filtering, washing, and drying the sample in a constant-temperature drying oven at 120 ℃ for 24H.
(3) After repeating the step (2) twice, the dried sample was calcined at 500 ℃ for 5 hours, and the obtained sample was labeled as C3.
The following example is an isopropanolamine synthesis
Example 4
21.8g of the prepared catalyst C1 was charged into the autoclave and replaced with nitrogen 3 times. 170.0g of liquid ammonia is firstly introduced, 48.3g of propylene oxide is then introduced, the temperature is raised to 60 ℃, and then the reaction is carried out for 2 hours under the condition of heat preservation. After the reaction is finished, cooling, deaminating and filtering, wherein the catalyst is recycled.
And (3) carrying out normal-temperature reduced pressure rectification (vacuum degree of minus 0.098MPa) on the filtered synthetic product to separate residual liquid ammonia, then heating to 112 ℃ for reduced pressure rectification (vacuum degree of minus 0.098MPa), and obtaining an isopropanolamine product at the tower top, wherein the product at the tower bottom is diisopropanolamine.
Example 5
The prepared 18.2g of C1 catalyst was charged into the autoclave and replaced 3 times with nitrogen. 170.0g of liquid ammonia is firstly introduced, 58.0g of propylene oxide is then introduced, the temperature is raised to 50 ℃, and then the reaction is carried out for 3 hours under the condition of heat preservation. After the reaction is finished, cooling, deaminating and filtering, wherein the catalyst is recycled. And (3) carrying out normal-temperature reduced pressure rectification (vacuum degree of minus 0.098MPa) on the filtered synthetic product to separate residual liquid ammonia, then heating to 112 ℃ for reduced pressure rectification (vacuum degree of minus 0.098MPa), and obtaining an isopropanolamine product at the tower top, wherein the product at the tower bottom is diisopropanolamine.
Example 6
The prepared 18.5g of C1 catalyst was charged into the autoclave and replaced 3 times with nitrogen. 170.0g of liquid ammonia is firstly introduced, 61.1g of propylene oxide is then introduced, the temperature is raised to 40 ℃, and then the reaction is carried out for 4 hours under the condition of heat preservation. After the reaction is finished, cooling, deaminating and filtering, wherein the catalyst is recycled. And (3) carrying out normal-temperature reduced pressure rectification (vacuum degree of minus 0.098MPa) on the filtered synthetic product to separate residual liquid ammonia, then heating to 112 ℃ for reduced pressure rectification (vacuum degree of minus 0.098MPa), and obtaining an isopropanolamine product at the tower top, wherein the product at the tower bottom is diisopropanolamine.
Example 7
The prepared 18.8g of C1 catalyst was charged into the autoclave and replaced 3 times with nitrogen. 170.0g of liquid ammonia is firstly introduced, 64.4g of propylene oxide is then introduced, the temperature is raised to 60 ℃, and then the reaction is carried out for 2 hours under the condition of heat preservation. After the reaction is finished, cooling, deaminating and filtering, wherein the catalyst is recycled. And (3) carrying out normal-temperature reduced pressure rectification (vacuum degree of minus 0.098MPa) on the filtered synthetic product to separate residual liquid ammonia, then heating to 112 ℃ for reduced pressure rectification (vacuum degree of minus 0.098MPa), and obtaining an isopropanolamine product at the tower top, wherein the product at the tower bottom is diisopropanolamine.
Example 8
The prepared 19.1g of C1 catalyst was charged into an autoclave and replaced with nitrogen 3 times. 170.0g of liquid ammonia is firstly introduced, 68.2g of propylene oxide is then introduced, the temperature is raised to 50 ℃, and then the reaction is carried out for 3 hours under the condition of heat preservation. After the reaction is finished, cooling, deaminating and filtering, wherein the catalyst is recycled. And (3) carrying out normal-temperature reduced pressure rectification (vacuum degree of minus 0.098MPa) on the filtered synthetic product to separate residual liquid ammonia, then heating to 112 ℃ for reduced pressure rectification (vacuum degree of minus 0.098MPa), and obtaining an isopropanolamine product at the tower top, wherein the product at the tower bottom is diisopropanolamine.
Example 9
14.6g of the prepared C1 catalyst were charged into the autoclave and replaced 3 times with nitrogen. 170.0g of liquid ammonia is firstly introduced, 72.5g of propylene oxide is then introduced, the temperature is raised to 40 ℃, and then the reaction is carried out for 4 hours under the condition of heat preservation. After the reaction is finished, cooling, deaminating and filtering, wherein the catalyst is recycled. And (3) carrying out normal-temperature reduced pressure rectification (vacuum degree of minus 0.098MPa) on the filtered synthetic product to separate residual liquid ammonia, then heating to 112 ℃ for reduced pressure rectification (vacuum degree of minus 0.098MPa), and obtaining an isopropanolamine product at the tower top, wherein the product at the tower bottom is diisopropanolamine.
Example 10
21.8g of the prepared catalyst C2 was charged into the autoclave and replaced with nitrogen 3 times. 170.0g of liquid ammonia is firstly introduced, 48.3g of propylene oxide is then introduced, the temperature is raised to 60 ℃, and then the reaction is carried out for 2 hours under the condition of heat preservation. After the reaction is finished, cooling, deaminating and filtering, wherein the catalyst is recycled. And (3) carrying out normal-temperature reduced pressure rectification (vacuum degree of minus 0.098MPa) on the filtered synthetic product to separate residual liquid ammonia, then heating to 112 ℃ for reduced pressure rectification (vacuum degree of minus 0.098MPa), and obtaining an isopropanolamine product at the tower top, wherein the product at the tower bottom is diisopropanolamine.
Example 11
The prepared 18.2g of C2 catalyst was charged into the autoclave and replaced 3 times with nitrogen. 170.0g of liquid ammonia is firstly introduced, 58.0g of propylene oxide is then introduced, the temperature is raised to 50 ℃, and then the reaction is carried out for 3 hours under the condition of heat preservation. After the reaction is finished, cooling, deaminating and filtering, wherein the catalyst is recycled. And (3) carrying out normal-temperature reduced pressure rectification (vacuum degree of minus 0.098MPa) on the filtered synthetic product to separate residual liquid ammonia, then heating to 112 ℃ for reduced pressure rectification (vacuum degree of minus 0.098MPa), and obtaining an isopropanolamine product at the tower top, wherein the product at the tower bottom is diisopropanolamine.
Example 12
The prepared 18.5g of C2 catalyst was charged into the autoclave and replaced 3 times with nitrogen. 170.0g of liquid ammonia is firstly introduced, 61.1g of propylene oxide is then introduced, the temperature is raised to 40 ℃, and then the reaction is carried out for 4 hours under the condition of heat preservation. After the reaction is finished, cooling, deaminating and filtering, wherein the catalyst is recycled. And (3) carrying out normal-temperature reduced pressure rectification (vacuum degree of minus 0.098MPa) on the filtered synthetic product to separate residual liquid ammonia, then heating to 112 ℃ for reduced pressure rectification (vacuum degree of minus 0.098MPa), and obtaining an isopropanolamine product at the tower top, wherein the product at the tower bottom is diisopropanolamine.
Example 13
The prepared 18.8g of C2 catalyst was charged into the autoclave and replaced 3 times with nitrogen. 170.0g of liquid ammonia is firstly introduced, 64.4g of propylene oxide is then introduced, the temperature is raised to 60 ℃, and then the reaction is carried out for 2 hours under the condition of heat preservation. After the reaction is finished, cooling, deaminating and filtering, wherein the catalyst is recycled. And (3) carrying out normal-temperature reduced pressure rectification (vacuum degree of minus 0.098MPa) on the filtered synthetic product to separate residual liquid ammonia, then heating to 112 ℃ for reduced pressure rectification (vacuum degree of minus 0.098MPa), and obtaining an isopropanolamine product at the tower top, wherein the product at the tower bottom is diisopropanolamine.
Example 14
The prepared 19.1g of C2 catalyst was charged into an autoclave and replaced with nitrogen 3 times. 170.0g of liquid ammonia is firstly introduced, 68.2g of propylene oxide is then introduced, the temperature is raised to 50 ℃, and then the reaction is carried out for 3 hours under the condition of heat preservation. After the reaction is finished, cooling, deaminating and filtering, wherein the catalyst is recycled. And (3) carrying out normal-temperature reduced pressure rectification (vacuum degree of minus 0.098MPa) on the filtered synthetic product to separate residual liquid ammonia, then heating to 112 ℃ for reduced pressure rectification (vacuum degree of minus 0.098MPa), and obtaining an isopropanolamine product at the tower top, wherein the product at the tower bottom is diisopropanolamine.
Example 15
14.6g of the prepared C2 catalyst were charged into the autoclave and replaced 3 times with nitrogen. 170.0g of liquid ammonia is firstly introduced, 72.5g of propylene oxide is then introduced, the temperature is raised to 40 ℃, and then the reaction is carried out for 4 hours under the condition of heat preservation. After the reaction is finished, cooling, deaminating and filtering, wherein the catalyst is recycled. And (3) carrying out normal-temperature reduced pressure rectification (vacuum degree of minus 0.098MPa) on the filtered synthetic product to separate residual liquid ammonia, then heating to 112 ℃ for reduced pressure rectification (vacuum degree of minus 0.098MPa), and obtaining an isopropanolamine product at the tower top, wherein the product at the tower bottom is diisopropanolamine.
Example 16
21.8g of the prepared catalyst C3 was charged into the autoclave and replaced with nitrogen 3 times. 170.0g of liquid ammonia is firstly introduced, 48.3g of propylene oxide is then introduced, the temperature is raised to 60 ℃, and then the reaction is carried out for 2 hours under the condition of heat preservation. After the reaction is finished, cooling, deaminating and filtering, wherein the catalyst is recycled. And (3) carrying out normal-temperature reduced pressure rectification (vacuum degree of minus 0.098MPa) on the filtered synthetic product to separate residual liquid ammonia, then heating to 112 ℃ for reduced pressure rectification (vacuum degree of minus 0.098MPa), and obtaining an isopropanolamine product at the tower top, wherein the product at the tower bottom is diisopropanolamine.
Example 17
The prepared 18.2g of C3 catalyst was charged into the autoclave and replaced 3 times with nitrogen. 170.0g of liquid ammonia is firstly introduced, 58.0g of propylene oxide is then introduced, the temperature is raised to 50 ℃, and then the reaction is carried out for 3 hours under the condition of heat preservation. After the reaction is finished, cooling, deaminating and filtering, wherein the catalyst is recycled. And (3) carrying out normal-temperature reduced pressure rectification (vacuum degree of minus 0.098MPa) on the filtered synthetic product to separate residual liquid ammonia, then heating to 112 ℃ and carrying out reduced pressure rectification (vacuum degree of minus 0.098MPa) to obtain an isopropanolamine product at the tower top, wherein the diisopropanolamine product at the tower bottom is diisopropanolamine.
Example 18
The prepared 18.5g of C3 catalyst was charged into the autoclave and replaced 3 times with nitrogen. 170.0g of liquid ammonia is firstly introduced, 61.1g of propylene oxide is then introduced, the temperature is raised to 40 ℃, and then the reaction is carried out for 4 hours under the condition of heat preservation. After the reaction is finished, cooling, deaminating and filtering, wherein the catalyst is recycled. And (3) carrying out normal-temperature reduced pressure rectification (vacuum degree of minus 0.098MPa) on the filtered synthetic product to separate residual liquid ammonia, then heating to 112 ℃ for reduced pressure rectification (vacuum degree of minus 0.098MPa), and obtaining an isopropanolamine product at the tower top, wherein the product at the tower bottom is diisopropanolamine.
Example 19
The prepared 18.8g of C3 catalyst was charged into the autoclave and replaced 3 times with nitrogen. 170.0g of liquid ammonia is firstly introduced, 64.4g of propylene oxide is then introduced, the temperature is raised to 60 ℃, and then the reaction is carried out for 2 hours under the condition of heat preservation. After the reaction is finished, cooling, deaminating and filtering, wherein the catalyst is recycled. And (3) carrying out normal-temperature reduced pressure rectification (vacuum degree of minus 0.098MPa) on the filtered synthetic product to separate residual liquid ammonia, then heating to 112 ℃ for reduced pressure rectification (vacuum degree of minus 0.098MPa), and obtaining an isopropanolamine product at the tower top, wherein the product at the tower bottom is diisopropanolamine.
Example 20
The prepared 19.1g of C3 catalyst was charged into an autoclave and replaced with nitrogen 3 times. 170.0g of liquid ammonia is firstly introduced, 68.2g of propylene oxide is then introduced, the temperature is raised to 50 ℃, and then the reaction is carried out for 3 hours under the condition of heat preservation. After the reaction is finished, cooling, deaminating and filtering, wherein the catalyst is recycled. And (3) carrying out normal-temperature reduced pressure rectification (vacuum degree of minus 0.098MPa) on the filtered synthetic product to separate residual liquid ammonia, then heating to 112 ℃ for reduced pressure rectification (vacuum degree of minus 0.098MPa), and obtaining an isopropanolamine product at the tower top, wherein the product at the tower bottom is diisopropanolamine.
Example 21
14.6g of the prepared C3 catalyst were charged into the autoclave and replaced 3 times with nitrogen. 170.0g of liquid ammonia is firstly introduced, 72.5g of propylene oxide is then introduced, the temperature is raised to 40 ℃, and then the reaction is carried out for 4 hours under the condition of heat preservation. After the reaction is finished, cooling, deaminating and filtering, wherein the catalyst is recycled. And (3) carrying out normal-temperature reduced pressure rectification (vacuum degree of minus 0.098MPa) on the filtered synthetic product to separate residual liquid ammonia, then heating to 112 ℃ for reduced pressure rectification (vacuum degree of minus 0.098MPa), and obtaining an isopropanolamine product at the tower top, wherein the product at the tower bottom is diisopropanolamine.
Comparative example 1
The prepared 18.2g of H-MOR was charged into an autoclave and replaced with nitrogen 3 times. 170.0g of liquid ammonia is firstly introduced, 58.0g of propylene oxide is then introduced, the temperature is raised to 60 ℃, and then the reaction is carried out for 2 hours under the condition of heat preservation. After the reaction is finished, cooling, deaminating and filtering, wherein the catalyst is recycled. And (3) carrying out normal-temperature reduced pressure rectification (vacuum degree of-0.098 MPa) on the filtered synthetic product to separate residual liquid ammonia, heating to 112 ℃, carrying out reduced pressure rectification (vacuum degree of-0.098 MPa) to obtain an isopropanolamine product on the tower top, and finally heating to 160 ℃, carrying out reduced pressure rectification (vacuum degree of-0.098 MPa) to obtain a diisopropanolamine product on the tower top, wherein the product in the tower bottom is triisopropanolamine.
Comparative example 2
Prepared 18.2g of water was charged into the autoclave, and replaced with nitrogen gas 3 times. 170.0g of liquid ammonia is firstly introduced, 58.0g of propylene oxide is then introduced, the temperature is raised to 60 ℃, and then the reaction is carried out for 2 hours under the condition of heat preservation. After the reaction is finished, cooling, deaminating and filtering, wherein the catalyst is recycled. And (3) carrying out normal-temperature reduced pressure rectification (vacuum degree of-0.098 MPa) on the filtered synthetic product to separate residual liquid ammonia, heating to 112 ℃, carrying out reduced pressure rectification (vacuum degree of-0.098 MPa) to obtain an isopropanolamine product on the tower top, and finally heating to 160 ℃, carrying out reduced pressure rectification (vacuum degree of-0.098 MPa) to obtain a diisopropanolamine product on the tower top, wherein the product in the tower bottom is triisopropanolamine.
The results of the synthetic experiments for examples 4-12 and comparative examples above are shown in Table 1:
in Table 1, MIPA is monoisopropanolamine, DIPA is diisopropanolamine, TIPA is triisopropanolamine, and PO is propylene oxide.
TABLE 1 results of examples and comparative examples
The embodiment and the comparative example show that the catalyst prepared by the invention has excellent activity and selectivity when being used for isopropanolamine synthesis, can effectively improve the proportion of monoisopropanolamine in a synthetic product, avoids generating triisopropanolamine and reduces the proportion of diisopropanolamine.
Claims (10)
1. The preparation method of the catalyst is characterized in that the catalyst is used for synthesizing isopropanolamine, and the preparation method of the catalyst comprises the following steps:
(1) dissolving water-soluble calcium salt in water to prepare calcium salt water solution;
(2) adding hydrogen mordenite into calcium salt water solution for excessive impregnation, stirring at constant temperature, filtering, washing, and drying;
(3) and (3) after repeating the step (2) for a plurality of times, roasting the dried sample to obtain the catalyst.
2. The production method according to claim 1,
the water-soluble calcium salt is calcium nitrate or calcium acetate.
3. The production method according to claim 1,
the concentration of the calcium salt aqueous solution is 0.1-0.3 mol/L.
4. The production method according to claim 1,
the temperature during constant-temperature stirring is 30-60 ℃, and the stirring time is 4-8 h.
5. The production method according to claim 1,
and during drying, the drying temperature is 100-120 ℃, and the drying time is 12-24 hours each time.
6. The production method according to claim 1,
the roasting temperature is 400-500 ℃, and the roasting time is 2-5 h.
7. The synthesis method of isopropanolamine is characterized by comprising the following steps:
(1) adding a catalyst into a high-pressure kettle, replacing the catalyst with nitrogen, introducing epoxypropane and liquid ammonia, heating to a set temperature, preserving heat, and reacting; the catalyst is prepared by the preparation method of any one of claims 1 to 6;
(2) after the reaction is finished, cooling, denitrifying, filtering, recovering the catalyst, and rectifying the filtrate under reduced pressure to obtain the isopropanolamine.
8. The method of synthesis according to claim 7,
no water is added in the synthesis process.
9. The method of synthesis according to claim 7,
in the step (1), the adding amount of the catalyst is 6-10% of the total mass of the epoxypropane and the liquid ammonia, and the molar ratio of the liquid ammonia to the epoxypropane is 8-12: 1.
10. The method of synthesis according to claim 7,
the set temperature is 40-60 ℃, and the reaction time is 2-4 h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111674635.6A CN114247470A (en) | 2021-12-31 | 2021-12-31 | Preparation method of catalyst and synthesis method of monoisopropanolamine |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111674635.6A CN114247470A (en) | 2021-12-31 | 2021-12-31 | Preparation method of catalyst and synthesis method of monoisopropanolamine |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114247470A true CN114247470A (en) | 2022-03-29 |
Family
ID=80799030
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111674635.6A Pending CN114247470A (en) | 2021-12-31 | 2021-12-31 | Preparation method of catalyst and synthesis method of monoisopropanolamine |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114247470A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115869960A (en) * | 2022-12-16 | 2023-03-31 | 南京红宝丽醇胺化学有限公司 | Ni-Co-Ce-Cr catalyst and preparation method and application thereof |
| CN116082172A (en) * | 2023-04-11 | 2023-05-09 | 山东友泉新材料有限公司 | Method for producing isopropanolamine |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050107637A1 (en) * | 2002-03-14 | 2005-05-19 | Till Gerlach | Catalysts and method for the production of amines |
| CN110193327A (en) * | 2019-07-08 | 2019-09-03 | 山东河清化工科技有限公司 | The non-aqueous monoisopropanolamine that catalyzes and synthesizes is from separator and its technique |
| CN110327967A (en) * | 2019-07-26 | 2019-10-15 | 山东达民化工股份有限公司 | The peaceful production. art of the isopropanol of catalyst and preparation method and application catalyst |
| CN112076780A (en) * | 2020-09-22 | 2020-12-15 | 山东达民化工股份有限公司 | Catalytic preparation method of isopropanolamine |
-
2021
- 2021-12-31 CN CN202111674635.6A patent/CN114247470A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050107637A1 (en) * | 2002-03-14 | 2005-05-19 | Till Gerlach | Catalysts and method for the production of amines |
| CN110193327A (en) * | 2019-07-08 | 2019-09-03 | 山东河清化工科技有限公司 | The non-aqueous monoisopropanolamine that catalyzes and synthesizes is from separator and its technique |
| CN110327967A (en) * | 2019-07-26 | 2019-10-15 | 山东达民化工股份有限公司 | The peaceful production. art of the isopropanol of catalyst and preparation method and application catalyst |
| CN112076780A (en) * | 2020-09-22 | 2020-12-15 | 山东达民化工股份有限公司 | Catalytic preparation method of isopropanolamine |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115869960A (en) * | 2022-12-16 | 2023-03-31 | 南京红宝丽醇胺化学有限公司 | Ni-Co-Ce-Cr catalyst and preparation method and application thereof |
| CN116082172A (en) * | 2023-04-11 | 2023-05-09 | 山东友泉新材料有限公司 | Method for producing isopropanolamine |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN114247470A (en) | Preparation method of catalyst and synthesis method of monoisopropanolamine | |
| CN112774726B (en) | Spherical titanium-silicon molecular sieve catalyst and preparation method thereof | |
| US8461391B2 (en) | Method for producing N,N-substituted-1,3-propandiamines | |
| CN112915993B (en) | Catalyst for coproduction of oxamide and methyl carbamate and preparation method thereof | |
| CN110590580B (en) | Preparation method of monoethanolamine and diethanolamine | |
| CN110639602B (en) | Catalyst for producing monoethanolamine and diethanolamine | |
| CN113398912A (en) | Catalyst for synthesizing dimethyl carbonate by alcoholysis of methyl carbamate | |
| CN110586175B (en) | Catalyst for increasing production of monoethanolamine and diethanolamine | |
| CN110590578B (en) | Method for preparing monoethanolamine and diethanolamine | |
| CN110586168B (en) | Catalyst for preparing monoethanolamine and diethanolamine | |
| CN110590579B (en) | Method for synthesizing monoethanolamine and diethanolamine | |
| CN110586169B (en) | Catalyst for synthesizing monoethanolamine and diethanolamine | |
| CN110590572B (en) | Method for producing monoethanolamine and diethanolamine | |
| CN110586171B (en) | Catalyst for producing monoethanolamine and diethanolamine | |
| CN110586170B (en) | Method for passivating catalysts of monoethanolamine and diethanolamine | |
| CN110639601B (en) | Catalyst for synthesizing monoethanolamine and diethanolamine | |
| CN110639600B (en) | Catalyst rich in monoethanolamine and diethanolamine | |
| CN110639605B (en) | Catalyst for increasing production of monoethanolamine and diethanolamine | |
| CN115197076B (en) | Preparation method of diethanol monoisopropanolamine | |
| CN110642730B (en) | Method for producing monoethanolamine and diethanolamine | |
| CN110642729B (en) | Method for synthesizing monoethanolamine and diethanolamine | |
| CN110642727B (en) | Method for increasing production of monoethanolamine and diethanolamine | |
| CN116237066A (en) | Solid strong acid catalyst and method for catalytic synthesis of 2, 2-di (2-furyl) propane by using same | |
| CN107915576A (en) | By the method for ethylene carbonate ester hydrolysis production ethylene glycol | |
| CN117205960A (en) | Method for synthesizing paraxylene by metal modified MCM-22 molecular sieve catalysis |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |