NL8403008A - PROCESS FOR PREPARING DIETHYLENE TRIAMINE. - Google Patents

Description

ί - 1 - -! "* · Ϊ"

Process for preparing diethylenetriamine.

The invention relates to a process for the preparation of diethylene triamine by ammonolysis of mono-ethanolamine.

Technically, diethylene triamine is prepared as a by-product in the preparation of ethylenediamine by reacting 1,2-dichloroethane with ammonia or by reacting monoethanolamine with ammonia. In the former process, a lot of sodium chloride, up to twice the molar amount of ethylenediamine, is formed as a by-product, and vinyl chloride is also formed as a by-product. Thus, the process becomes expensive due to waste processing, and has the drawback that the equipment is severely corroded by chloride ions. Furthermore, in both processes, the preparation of diethylenetriamine depends on the demand for ethylenediamine.

A method of reacting monoethanolamine with ethylene diamine with a phosphorus compound such as phosphoric acid catalyst (Japanese Patent No. 6982/1981) and reacting monoethanolamine with ethylene diamine in the liquid has also been described for preparing diethylene triamine phase with an inorganic compound containing alumina or silicon dioxide as the major constituent as the catalyst (Japanese Patent Application Laid-open No. 38329/1980). However, these processes have not yet achieved the desired selectivity and productivity because, in addition to the fact that ethylenediamine is relatively expensive, the conversion of ethylenediamine and the selectivity to diethylene triamine are both small.

The process described in Japanese Patent Application Laid-open No. 52322/1983 improves the process described in Japanese Patent No. 6982/1981 above and yields non-cyclic amines in good yield while simultaneously controlling the formation of cyclic amines by adding an amount of ammonia that is 0.5-10 times the 8403008% - 2% molar amount of monoethanolamine in the reaction of monoethanolamine with ethylenediamine with a phosphorus compound such as phosphoric acid as a catalyst. However, in this method, the selectivity for diethylene triamine is not sufficient and monoethanolamine, ethylenediamine and ammonia are consumed to prepare diethylene triamine using the expensive ethylene diamine as a starting material.

It was discovered that diethylene triamine could be produced remarkably selectively by reacting ammonia and monoethanol-10 amine in the presence of a. phosphorus compound and ethylenediamine under certain conditions.

The process of the invention relates to the preparation of diethylene triamine by reaction of ammonia with monoethanolamine in the presence of a phosphorus compound 15 and ethylenediamine in a molar ratio of ammonia to monoethanolamine of at least 11: 1.

The phosphorus compounds to be used in the invention are, for example, various salts of phosphoric acid, pyrophosphates, compounds of phosphoric acid or anhydrides thereof, phosphorous or anhydrides thereof, alkyl or aryl esters of phosphoric acid or phosphorous acid, and alkyl or aryl phosphoric acid or phosphorous acid. This substance can be used alone or in a mixture.

Of the various salts of phosphoric acid, dihydrogen phosphates or pyrophosphates obtained therefrom are preferred. To be used dihydrogen phosphates are for instance: ammonium, lithiumdiwaterstof-phosphate, natriumdiwaterstoffosfkat, potassium dihydrogen phosphate, ruhidiumdiwaterstoffosfaat, cesiumdiwaterstoffosfaat, beryllium-dihydrogen phosphate, magnesium dihydrogen phosphates, calciumdiwater-30 phosphate, strontiumdiwaterstoffosfaat, bariumdiwaterstof phosphate, and bet reaction product of a rare earth compound with phosphoric acid, said compound being an atomic ratio of has from phosphorus, to rare earth element of 3: 1, such as the reaction product of phosphoric acid with the hydroxide or oxide of elements such as scandium, yttrium, lanthanium, cerium, praseodymium, neodymium, 8403008 ^ * - 3 - promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium. Also to be used are manganese dihydrogen phosphate, iron dihydrogen phosphate, cobalt dihydrogen phosphate, zinc dihydrogen phosphate, admium dihydrogen phosphate, aluminum dihydrogen phosphate, thallium dihydrogen phosphate, tin dihydrogen phosphate, lead dihydrogen phosphate, and lead dihydrogen phosphate, lead dihydrogen phosphate, and lead dihydrogen phosphate, has an atomic ratio of phosphorus to metal of 3: 1, such as the reaction product of phosphoric acid 10 with the hydroxide or oxide of said metal. Other examples are the reaction product of a nickel or copper compound with phosphoric acid, which product has an atomic ratio of phosphorus to metal of 2: 1, such as the reaction product of phosphoric acid with the hydroxide or oxide of said metal.

Acid pyrophosphates obtained by dehydration of the above dihydrogen phosphates or equivalent compounds can also be used. Furthermore, one can use the reaction product of phosphoric acid with a compound of a metal of the iVa or Va group of the periodic table, for example a product with an atomic ratio of P / Ti = 2, P / Zr = 2, P / Hf = 2, P / V = 2, P / Nb = 3, or P / Ta = 3, such as titanyl dihydrogen phosphate or zircony dihydrogen phosphate.

Monohydrogen phosphates can also be used. Examples of mono-hydrogen phosphates are diammoniumwaterstof-25 phosphate, berylliumwaterstoffosfaat, magnesium hydrogen phosphate, calcium hydrogen phosphate, strontium hydrogen phosphate, barium hydrogen phosphate, scandiumwaterstoffosfaat, yttriumwaterstoffosfaat, lanthaniumwaterstoffosfaat, ceriumwaterstoffosfaat, praseodymiumwaterstoffosfaat, neodymium dihydrogen phosphate, pro-30 methiumwaterstoffosfaat, samariumwaterstoffosfaat, europium water tof phosphate, gadoliniumwaterstoffosfaat, terbiumwaterstof- phosphate, dysprosiumwaterstoffosfaat, holmiumwaterstoffostaat, erbiumwaterstoffosfaat, thuliumwaterstoffosfaat, ytterbium-waters toffos phosphate, lutetiumwaters toffosfaat, chroomwaterstoffos-35 phosphate, manganese hydrogen phosphate, iron hydrogen phosphate, cobalt 8,403,008 ύ * »- 4 - hydrogen phosphate, nickel hydrogen phosphate, copper hydrogen phosphate, silver hydrogen phosphate, zinc hydrogen phosphate, cadmiumwaterstoffos phosphate , mercury hydrogen phosphate, aluminum hydrogen phosphate, gallium hydrogen phosphate, indium hydrogen osphate, thallium hydrogen phosphate, tin hydrogen phosphate, lead hydrogen phosphate, antimony hydrogen phosphate and bismuth hydrogen phosphate. It is also possible to use the reaction product of phosphoric acid with a compound of a metal of the IVa or Va group of the periodic table, for example a product with an atomic ratio of P / Ti = 1.10 P / Zr = 1, P / Hf = 1 , P / V = 1.5, P / Nb = 1.5 or P / Ta = 1.5.

Moreover, one can use normal salts of phosphoric acid, for example, boron phosphate, scandiumfosfaat, yttrium phosphate, lanthanumfosfaat, cerium phosphate, praseodymiumfosfaat, neodymium phosphate, promethiumfosfaat, samariumfosfaat, europium-15 phosphate, gadolinium phosphate, terbiumfosfaat, dysprosiumfosfaat, holmiumfosfaat, erbiumfosfaat, thuliumfosfaat, ytterbiumfosfaat, lutetiumfosfaat , chromium phosphate, iron phosphate, aluminum phosphate and bismuth phosphate.

The following phosphoric acid derivatives can be used; orthophosphoric acid, pyrophosphoric acid, metaphosphoric acid and condensed phosphoric acids such as polyphosphoric acid.

As the phosphorous acid compound, orthophosphorous acid itself is used in particular. Furthermore, mono-, di-, trialkylic aryl esters of phosphoric or phosphorous acid can be used as the catalyst of the invention, the alkyl groups preferably having 1-8 carbon atoms and the aryl groups having 6-20 carbon atoms. i.e. a phenyl or an alkylphenyl group.

For example, one can use triethyl phosphate, triethyl phosphite, phenyl phosphate or phenyl phosphite.

As alkyl or aryl phosphoric acid or phosphorous acid, where the alkyl and aryl groups preferably have 1-8 carbon atoms and 6-20 carbon atoms, for example, phenylphosphinic acid, ethylphosphinic acid, phenylphosphonic acid and naphthaphosphonic acid may be exemplified.

Among the above phosphorus compounds, di-8403008-5 hydrogen phosphates, phosphates of vanadium compounds and phosphates of rare earth compounds are especially preferred.

The amount of the above phosphorus compound used as a catalyst may be 0.01-1 mole based on the phosphorus content per 1 mole of monoethanolamine as a starting material. Less than 0.01 mole does not provide sufficient activity while more than 1 mole is unnecessary.

One usually adds one to the invention. amount of ethylenediamine of 0.1-5 mol per 1 mol of mono-ethanolamine.

If less than 0.1 mole of ethylenediamine is added, the selectivity to diethylenetriamine deteriorates due to the formation of the byproducts of ethylenediamine, aminoethylethanolamine, piperazine or aminoethylpiperazine. On the other hand, if more than 5 moles of ethylenediamine are added, the selectivity for diethylene triamine no longer increases significantly, while the volume efficiency of the reactor deteriorates.

It is therefore preferable to add 1-2 moles of ethylenediamine.

In the process of the invention, ammonia and monoethanolamine are reacted with each other in a molar ratio of ammonia to monoethanolamine of at least 11: 1. If they react in a ratio less than 11: 1, a large amount of ethylenediamine is consumed, so the process is unsuccessful. The molar ratio is preferably 11: 1 - 30: 1.

The greater the molar ratio, the better the selectivity for diethylene triamine, but the poorer the volume efficiency of the reactor. The reaction temperature is usually set at 200-400 ° C. Below 200 ° C, the reaction rate becomes slower, while above 400 ° C, the thermal decomposition of diethylene triamine increases. Preferably the temperature is 250-300 ° G.

Although the reaction time depends on the amount of catalyst used and the reaction temperature, 30 minutes-8 hours is usually sufficient.

The reaction can be carried out either in the liquid phase or in the gas phase, but preferably in the liquid phase, the pressure usually being kept at least 200 kg / cm. Since cyclic compounds such as piperazine and aminopiperazine are produced in large quantities in the gaseous phase, the reaction in the liquid phase is preferred.

In carrying out the process, both the batch and continuous systems operate acceptable, but the fixed bed continuous system is preferred in view of the separation of the spent catalyst. In this case, a spatial flow rate of the reagents of 0.1-10 g total amount of reagents / ml catalyst volume / hour, preferably 0.2-2, is used.

The above catalyst can be supported on a support such as kieselguhr, silicon dioxide or aluminum oxide.

The diethylene triamine produced can be easily separated from the mixture, for example, by distillation.

Since the process of the invention has allowed a preparation of diethylene triamine from ammonia and monoethanolamine to consume substantially no expensive ethylenediamine, which is added in this invention but is not used as a raw material, the process has great industrial value.

Example I 25

18.3 g of monoethanolamine (0.3 mole), 18.0 g of ethylenediamine (0.3 mole) and 3.18 g of aluminum dihydrogen phosphate (0.03 mole as P) were introduced into a 300 ml capacity autoclave with a magnetic stirrer. After the air in the autoclave 30 was replaced by nitrogen, 56.2 g of liquid ammonia (3.3 mol) was added and the mixture was heated to 270 ° C and then kept at that temperature for 3 hours, the pressure being 280 kg / cm. The reaction mixture was then cooled to room temperature, the pressure lowered, and the resulting solution analyzed by gas chromatography.

8403008 £ -¾ - 7 -

Conversion of monoethanolamine 81 Z

Selectivity to diethylenetriamine 70% Under the above conditions (molar ratio of ammonia to monoethanolamine of 11: 1) ethylenediamine remained in the reaction mixture in the same amount, as added, 18.0 g. This means that diethylenetriamine was synthesized by the reaction with only monoethanolamine and ammonia as starting materials.

Example II

The procedure described in Example I was repeated except that the amount of liquid ammonia was 66.4 g (3.9 mol).

Conversion of monoethanolamine 76%

Selectivity to diethylenetriamine 74% 20

Selectivity to ethylenediamine 2%

Under the above conditions (molar ratio of ammonia to monoethanolamine of 13: 1), the amount of ethylenediamine increased compared to before the reaction. The ethylene diamine increase was 2.0% based on the converted monoethanolamine.

Example III

The procedure described in Example I was repeated except that the amount of liquid ammonia was 76.6 g (4.5 mol) j.

35 y 8403008 - 8 -

Conversion of monoethanolamine 72%

Selectivity to diethylene tri amine 77%

Selectivity to ethylenediamine · 4% 5

Control I

The procedure described in Example I was repeated except that the amount of liquid ammonia was 46.0 g (2.7 mol).

Conversion of monoethanolamine 86%

Selectivity to diethylene,. tri amine 64% 10

Under the above conditions (molar ratio of ammonia to monoethanolamine of 9: 1), the amount of ethylenediamine decreased compared to before the reaction. The amount of ethylenediamine consumed was 2% based on the converted monoethanolamine.

Examples IV-XXIV

The procedure described in Example I was repeated except that several other catalysts were used, the amount of which was 0.03 mole calculated as P. The results are shown in Table A. 1 8403008 - 9 - i c <u μ 0}

• H rH

Φ μ Λ, • η μ α) £ .μ cn co r> oo on σ> - ^ 2 S 2 - - UMÊ - - "^ u a Φ. U Γμ ϋ μ« Shi co ο μ>

- ° L

• rl a <u a) μ <u

• pIHK

. -Η Λ <U

g 3 ^ .5ο - ^^ ~ - ~ οο ~ σ ° - h <u g 0 r-i μ to u φ ο · μ cd co ο Ό co>>.

I — I

β, μ ι «β, ϋ -1-1¾ • μ α) φ φ τ-4 -ο μ>, ε ~ ϊ β ή ύ φ> μ 2 · μ Φ β d ^ '-ö' s ^ 00 νο Γ-. co ο - <r ο Ο ^ 2 2 2 'cB ^ iïoS'or ^ r ^ vovor-.inr -.- ^ ρ ^' β'β ο ri μ · μ co (U ο μ u co ο μ φ> <> Γ-ι μ <US - • s 6 s,

cd Λ I

Ε-ι φ> -μ β ο • μ ω ö Β β β § · μχκ 1 Jllsssasssisssssss β SOË Φ Ο Β β r-c »β μ φ« τ-Ι Τ3 _ cn! S Μ m m £> g 8 g λ Λ Ν ° N ° Ν «'t ^ g> s, 3 * ο- ο * ς * I s? . ? ? ο-? 1 I1>> S '**. ο * g £, ο-% s 3 2 2 J? δ ^ * „ο- Β« Ν 5%, δ 5

(¾ 5 n * iSÉ3 £ 3io «<3> JI *« * S

ti r-c φ φ ιβ ι_ι Η · “*

_1 ι_1 WHt> MH

g Η >>>;> ΗΧΧΧΧ> <ίΡ <>!> <'! *! π «-> *" \ Λ.,. ϊ <Μ Η -10- \ o on oo on o rs. ir> i— * - * -> CM * - »ο ο and ο ο ο on ο ο -ο · - ο ο ο (Η ^ ΟΓ ^, Γ ^ νΟΌΌΌ 4) · «Η 60 Γ“ ί Ο> Μ α)> 1-. And r * · ιΛ Ο Ό ο σ> οο γ «νο οο οο σ« ι— (5-ι on 0) a / -s öo a

S3 ¢ 8 N

ο ο a

w CM · ι- (O

a / s r — t M- {u st on «h ra

I O <f r'- / -s ra O

S3 · PU OO on I Mf O CM CU CM o sr rH PU W CM PU PU O> ·, on s ^ ® uj w pu ö pc -Q r-ι cu.-T on ra m Pu HF = <<1 PC 'ti

Η H

Η Η H>

Η> <ί Η Η Η H

a s s s sö s 84 0 3 0 0 8 -11-

Coatrole II

Mea charged 18.3 g (0.3 mole) of monoethanolamine, 18.0 g (0.3 mole) ethylenediamine and 0.03 mole calculated as P 5 lanthanum phosphoric acid catalyst (the P / La mole ratio was 3: 1) in an autoclave with a capacity of 300 ml with a magnetic! stirrer. After the air in the autoclave was replaced with nitrogen, 25.5 g (1.5 mol) of liquid ammonia was added and the mixture was heated to 270 ° C and then kept at that temperature for 3 hours. The reaction mixture was then cooled to room temperature, the pressure lowered, and the resulting solution analyzed by gas chromatography.

Conversion of monoethanolamine 100% 15 Selectivity to diethylene triamine 33%

Selectivity "for triethylenetetramine 8%

Selectivity for piperazine 14%

Selectivity for aminoethylpiper-20 azine 17%

Under the above conditions (molar ratio of ammonia to monoethanolamine of 5: 1), 22% ethylenediamine was consumed based on the converted monoethanolamine.

Furthermore, the selectivity to diethylene triamine was greatly reduced and large amounts of cyclic compounds such as piperazine and aminoethylpiperazine were produced.

Control III

3 °:

The procedure described in Example X was repeated except that no ethylenediamine was added.

Conversion of monoethanolamine 65%. Selectivity for diethylene tri-.

amine J 32 * 8403008 -12-

Selectivity to ethylene diamine 44%

In this case, the selectivity for diethylene-5 triamine was also low, while ethylene diamine was produced in a large amount.

Example XXV

10 Preparation of the Catalyst.

112.8 g of lanthanum nitrate hexahydrate were dissolved in 300 ml of water to which 168 g of kieselguhr was added. While stirring the slurry, 449.5 g of a 20% aqueous solution of ammonium dihydrogen phosphate was added thereto. After the solution was heated and the water evaporated, it was dried at 120 ° C for 3 hours and then baked at 400 ° C for 3 hours.

20 Preparation of Djethylenetriamine.

150 ml of the thus prepared catalyst, of 1.2-1.7 mm, atomic ratio P / La of 3: 1, and La ^ PO ^) ^ equivalent of 40%, on kieselguhr as carrier, were used as filling for 25 a stainless steel reactor with an internal diameter of 15 mm and a length of 1 m. Ammonia, monoethanolamine and ethylenediamine were fed in mol ratio NH 2 / monoethanolamine 18: 1 and ethylenediamine / monoethanolamine 2: 1 and at a flow rate of the mixed feed of 1 g / ral catalyst / hour.

The reactor was kept at 260 DEG C. and the reaction pressure. at 320 kg / cm.

The reaction mixture was analyzed with the following results:

Conversion of monoethanolamine 65% 35 Selectivity to diethylene triamines -7 91% 8403008 -13-

Selectivity to Triethylenetetramine 6%

Selectivity to ethylenediamine 2% 5

A combination of fixed bed and continuous system as used in this example is preferred for the industrial production of diethylene triamine using the invention.

10 If one has higher polyamines than diethylenetriamine.

if desired, they can also be produced in sufficient yield by recycling the diethylene triamine thus produced to the reactor.

15 y

-. * 4 * 4 ύ λ Q

"J". J V \ J Q

Claims (7)

1. Process for preparing diethylenetriamine by reaction of ammonia with monoethanolamine characterized in that the reaction is carried out at a molar ratio of ammonia to monoethanolamine of at least 11: 1 in the presence of a phosphorus compound. and ethylenediamine. Process according to claim 1, characterized in that the mol ratio is 11: 1-30: 1. Process according to claim 1, characterized in that the reaction is carried out in the liquid phase. Method according to claims 1-3, characterized in that the reaction is carried out in a fixed bed. Method according to claims 1-4, characterized in that the reaction is carried out in a continuous system. 6. Method according to claims 1-5, characterized in that the phosphorus compound is a dihydrogen phosphate. A method according to claims 1-6, characterized in that the phosphorus compound is a rare earth metal phosphate. 1 8403008