CN1258399C - Oxydation catalyst used in synthesizing 4-hydroxy 3-methoxy benzaldehyde and 4-hydroxyl-3-ethoxy benzaldehyde by glyoxalic acid method - Google Patents

Abstract

The present invention relates to an oxidation catalyst for synthesizing 4-hydroxy-3-methoxybenzaldehyde and 4-hydroxy-3-ethoxyphenyl methanal by a glyoxalic acid method. The composition formula used for indicating elements and molar content thereof of the catalyst composition is Mg<0 to 0.3>. Mo<0 to 0.02>.Fe<0.03 to 0.3>.Cu<0.004 to 0.04>.Zn<0.002 to 0.07>. Al<0 to 0.7>.K<0.009 to 0.4>. Na<0 to 0.03>.O<0.1 to 3.0>. S <0.05 to 0.9>. The present invention has the preparation method that a required amount of aluminum oxide or/and iron oxide is used as raw material (I); a required amount of sodium salt of a molybdenum element and a required amount of sulfate of other metallic elements are used as raw material (II); the raw material (I) and the raw material (II) are uniformly mixed and are milled by a ball mill for 1h to obtain the required catalyst. The oxidizing yield of 4-hydroxy-3-methoxybenzaldehyde and 4-hydroxy-3-ethoxyphenyl methanal is higher than that of a Na type catalyst. Each group of the catalysts are used for filtering 4 tons of material, the time can be saved by 220 minutes, and the number of net clearing time is 1/4 of that of the Na type catalyst.

Description

The oxidation catalyst of the synthetic 4-hydroxy 3-methoxybenzene formaldehyde of acetaldehyde acid system and 4-hydroxyl-3-ethoxy-benzaldehyde

Technical field

The present invention relates to the needed oxidation catalyst of acetaldehyde acid system synthesis of vanillin and Ethyl vanillin, promptly relate to the synthetic 4-hydroxy 3-methoxybenzene formaldehyde of a kind of acetaldehyde acid system, the 4-hydroxyl-needed oxidation catalyst of 3-ethoxy-benzaldehyde.

Background technology

Vanillic aldehyde (vanillic aldehyde), its formal name used at school are 4-hydroxy 3-methoxybenzene formaldehyde, are a kind of fumet, as food flavor; Ethyl vanillin, formal name used at school are 4-hydroxyl-3-ethoxy-benzaldehyde, also are a kind of fumet, and its fragrance is higher 3～4 times than vanillic aldehyde, also are used as food flavor etc.

1. synthesis of vanillin: acetaldehyde acid system synthesis of vanillin is to be raw material with glyoxalic acid and guaiacol, and through condensation, oxidation, decarboxylation and make, its chemical equation (main reaction) is as follows:

1.1 condensation reaction

Guaiacol glyoxalic acid 4-hydroxyl-3-methoxyl group mandelic acid (mandelic acid)

1.2 oxidation reaction

4-hydroxyl-3-methoxyl group mandelic acid 4-hydroxy 3-methoxybenzene acetonic acid

1.3 decarboxylic reaction

4-hydroxy 3-methoxybenzene acetonic acid vanillic aldehyde

2, synthetic Ethyl vanillin: the synthetic ethyl of acetaldehyde acid system is fragrant plain, is that more to create this phenol with glyoxalic acid and ethyl be raw material, makes through condensation, oxidation, decarboxylation, and its chemical equation (main reaction) is as follows:

2.1, condensation reaction

Guaethol glyoxalic acid 4-hydroxyl-3-ethyoxyl mandelic acid (ethyl mandelic acid)

2.2, oxidation reaction

4-hydroxyl-3-ethyoxyl mandelic acid 4-hydroxyl-3-ethoxybenzene acetonic acid

2.3, decarboxylic reaction

4-hydroxyl-3-ethoxybenzene acetonic acid Ethyl vanillin

At present, producing vanillic aldehyde and Ethyl vanillin, generally to adopt copper sulphate be oxidation catalyst, and the copper sulphate consumption is big, after air oxidation a few hours, is reduced into cuprous oxide, the subparticle that takes on a red color, and its active decline needs the long period during filtration, and filter screen cleans frequent; Now adopt Na type oxidation catalyst, activity and selectivity are all better, but after being used for suitability for industrialized production, filtration difficulty, filter screen are easily blocked, and wash number influences more produces normal operation.

Summary of the invention

The objective of the invention is to overcome the deficiency that prior art exists, provide a kind of active selectivity all preferably, the oxidation catalyst that is applicable to acetaldehyde acid system synthesis of vanillin and Ethyl vanillin of soluble, easy filtration.

The objective of the invention is to adopt following technical scheme to realize.

The oxidation catalyst of a kind of acetaldehyde acid system synthesis of vanillin and Ethyl vanillin in order to the element of this carbon monoxide-olefin polymeric of statement formation and the composition formula of molfraction thereof is:

(Mg) _a·(Mo) _b·(Fe) _c·(Cu) _d·(Zn) _e·(Al) _f·(K) _g·(Na) _h·O _x·S _y

In the formula, a, b, c, d, e, f, g, h, x and y are respectively the molfraction of Mg, Mo, Fe, Cu, Zn, Al, K, Na, O and S element, wherein,

The a value is that 0～0.3 b value is that 0～0.02 c value is 0.03～0.3

The d value is that 0.004～0.04 e value is that 0.002～0.07 f value is 0～0.7

The g value is that 0.009～0.4 h value is that 0～0.03 x value is 0.1～3

The y value is 0.05～0.9

This Preparation of catalysts method is as follows:

With the aluminium oxide of requirement or/and the iron oxide of requirement is raw material (I); The sulfate of getting required other metallic elements of the sodium salt of Mo element of requirement and requirement more respectively is raw material (II); Fully mix with raw material (I) with (II), add to ball milling 1h in the ball grinder then, make required oxidation catalyst.

The molfraction of each element is respectively in the above-mentioned oxidation catalyst:

The a value is that 0.02～0.15 b value is that 0.003～0.015 c value is 0.04～0.25

The d value is that 0.006～0.035 e value is that 0.003～0.05 f value is 0～0.3

The g value is that 0.01～0.3 h value is that 0.006～0.02 x value is 0.20～2.50

The y value is 0.09～0.5

Introduce the preparation method of oxidation catalyst of the present invention below:

1, Preparation of Catalyst

Get the aluminium oxide (Al of requirement ₂O ₃) or/and the iron oxide (Fe of requirement ₂O ₃) in any is raw material (I); The sulfate of getting needed other metallic elements of sodium (Na) salt of molybdenum (Mo) element of requirement and requirement is raw material (II); With raw material (1) with (II) fully behind the mixing, be added to interior the ball milling 1h of self-control ball grinder (15 of volume 20L, 120 rev/mins, φ 35mm ball, 30 in φ 25mm ball), tell abrading-ball, the collection product makes required catalyst.

2, catalyst is used:

The application of the oxidation catalyst that the present invention makes is at Φ 80mm, in the glass oxidizing tower of H=1200mm, realization gas, liquid, solid three-phase bubbling oxidation reaction.The condensation liquid mandelic acid (or ethyl mandelic acid) that a certain amount of catalyst, glyoxalic acid and guaiacol (or guaethol) condensation reaction of packing in this tower obtains, with the amount bubbling air of 180～200L/h, carried out oxidation reaction 7～8 hours in 93 ± 2 ℃; Then through intensification decarboxylation, filtration.By existing method, analyze vanillic aldehyde (or Ethyl vanillin) content in the oxidation liquid, calculate its oxidization-hydrogenation ratio.Discard filter cake, filtrate makes vanillic aldehyde (or Ethyl vanillin) by prior art through extraction, distillation, recrystallization.

Producing the filtration of hundred tonnes Ethyl vanillin (or kiloton vanillic aldehyde) per year, is to adopt ZTB-II type four pocket type accurate filters, its Φ=550mm, and H=200mm, volume are 0.76m ³, filter screen is the white steel meshes of 150 orders (0.1mm), filter pressure is 0.5～0.6Mpa.4 tons of materials of every batch of filtration filtered and finish in 20 minutes, filtered 15～20 batches of cleaning primary filter screens that stop.

The present invention adopts above-mentioned technical scheme, compared with prior art has following advantage:

(1) oxidation catalyst industrial applications of the present invention shows, its methyl vanillin and Ethyl vanillin oxidization-hydrogenation ratio all are higher than used Na type catalyst.

(2) industrial production adopts ZTB-II type four pocket type accurate filters as previously mentioned, and every batch is filtered 4 tons of materials, needs 240 minutes with Na type oxidation catalyst, and filter 23～4 batch materials need stop, the cleaning primary filter screen; Oxidation catalyst of the present invention is a solubility, filters easily, filters a batch materials about 20 minutes, filters 15～20 batches of parkings, and the cleaning primary filter screen makes the time of finishing a collection of 4 tons of material filterings, has shortened 220 minutes (3～4 hours).

The specific embodiment

Now the present invention is further described as follows in conjunction with the specific embodiment:

Embodiment 1

(1) Preparation of Catalyst

Get 2g iron oxide (Fe ₂O ₃) be raw material (I); Take by weighing 16.62g ferric sulfate (Fe ₂(SO ₄) ₃XH ₂O contains Fe21%), 1.17g potassium sulfate (K ₂SO ₄), 1.17g copper sulphate (CuSO ₄Anhydrous), 1.03g zinc sulfate (ZnSO ₄7H ₂O) be raw material (II), it mixed join the interior ball milling 1h of ball grinder (15 of volume 20L, 120 rev/mins, φ 35mm ball, 30 in φ 25mm ball), tell abrading-ball, collect product, make required catalyst, this carbon monoxide-olefin polymeric composition formula is:

Fe _0.08·Cu _0.007·Zn _0.004·K _0.01·O _0.49·S _0.11

(2) catalyst is used

The above-mentioned oxidation catalyst that makes, glyoxalic acid and guaiacol (or guaethol) reaction are made condensation liquid mandelic acid (or ethyl mandelic acid), put into Φ 80mm, in the glass oxidizing tower of H1200mm, amount bubbling air in condensation liquid with 190 ± 10ml/h, and in 93 ± 2 ℃ of reaction 7～8h, decarboxylation, filtration then heat up.Analyze vanillic aldehyde (or Ethyl vanillin) content in the oxidation liquid.Discard filter cake, filtrate makes vanillic aldehyde or Ethyl vanillin by known method through extraction, distillation, recrystallization.Catalyst and condensation liquid consumption, mandelic acid or ethyl mandelic acid content, and product oxidization-hydrogenation ratio etc. sees Table 1, example 1 corresponding experiment lot number in the table 2.

Embodiment 2

(1) Preparation of Catalyst

Get 10g aluminium oxide (Al ₂O ₃), 5g iron oxide (Fe ₂O ₃) be raw material (I); Get 1.2g sodium molybdate (Na ₂MoO ₄2H ₂O) and 10g potassium sulfate (K ₂SO ₄), 6g copper sulphate (CuSO ₄5H ₂O), 10g zinc sulfate (ZnSO ₄7H ₂O), 35.2g ferric sulfate [Fe ₂(SO ₄) ₃XH ₂O], 10.8g magnesium sulfate (MgSO ₄7H ₂O) be raw material (II); With raw material (I) and the abundant mixing of raw material (II), join ball milling 1h in the ball grinder then, tell abrading-ball, collect product and be the oxidation catalyst that makes.Its composition formula is:

Fe _0.2·Cu _0.02·Zn _0.03·Mg _0.04·Mo _0.005·Al _0.2·K _0.1·Na _0.009·O _1.84·S _0.36.

(2) catalyst is used

Above-mentioned catalyst, glyoxalic acid and the guaiacol (or guaethol) of making reacted the condensation liquid adding φ 80mm that makes, in the glass oxidizing tower of H1200mm, amount bubbling air in condensation liquid with 190 ± 10ml/h, and in 93 ± 2 ℃ of reaction 7-8h, press known method intensification decarboxylation, filtration then, and analyze vanillic aldehyde (or Ethyl vanillin) content in the oxidation liquid, calculate oxidization-hydrogenation ratio, discard filter cake, filtrate makes vanillic aldehyde (or Ethyl vanillin) through extraction, distillation, recrystallization.Wherein condensation liquid, catalyst amount; Mandelic acid or ethyl mandelic acid content etc. see Table 1, example 2 corresponding experiment lot numbers in the table 2.

Embodiment 3

(1) Preparation of Catalyst

Carry out according to embodiment 2 preparation technologies.Get 1gFe ₂O ₃Be raw material (I); Take by weighing 10gK again ₂SO ₄, 6gCuSO ₄5H ₂O, 10gZnSO ₄7H ₂O, 35.2gFe ₂(SO ₄) ₃XH ₂O, 10.8gMgSO ₄7H ₂O, 2gNa ₂MoO ₄2H ₂O is raw material (II); With the abundant mixing of raw material (I) and raw material (II), with ball grinder ball milling 1h, tell abrading-ball, collect product, make required catalyst.The composition composition formula of this catalyst is:

Fe _0.1·Cu _0.02·Zn _0.03·Mg _0.04·Mo _0.008·K _0.1·Na _0.02·O _1.49·S _0.20

(2) catalyst is used

The Application of Catalyst method that makes above is with embodiment 2 they (2).Wherein catalyst, condensation liquid consumption and mandelic acid or ethyl mandelic acid content etc. see Table 1, embodiment 3 corresponding lot numbers in the table 2.

Embodiment 4

(1) Preparation of Catalyst

The preparation method is with embodiment 2 described technologies.Take by weighing 5.1gAl ₂O ₃Be raw material (I); Take by weighing 17.4gK again ₂SO ₄, 7.5gCuSO ₄5H ₂O, 11.5gZnSO ₄7H ₂O, 142.83gFe ₂(SO ₄) ₃XH ₂O, 24.6gMgSO ₄7H ₂O, 2.4g Na ₂MoO ₄2H ₂O is raw material (II); With the abundant mixing of raw material (I) and raw material (II), be added to processing in the ball grinder (see and go up example).The composition formula of the carbon monoxide-olefin polymeric that makes is:

Fe _0.15·Cu _0.03·Zn _0.04·Mg _0.1·Mo _0.01·K _0.2·Na _0.02·Al _0.1·O _2.17·S _0.39

(2) catalyst is used

The above-mentioned catalyst that makes, its application process is with embodiment 2 they (2).Wherein catalyst and condensation liquid consumption, the content of mandelic acid or ethyl mandelic acid etc. are listed in table 1 and the table 2 respectively.See corresponding lot number among table 1, table 2 embodiment 4 for details.

Table 1 is with the oxidation reaction result of oxidation catalyst synthesis of vanillin of the present invention

Embodiment	The experiment lot number	Condensation liquid				Oxidation liquid			Oxidization-hydrogenation ratio (%)	Catalyst addition (g)
											Condensation liquid weight (g)	Mandelic acid content (%)	Mandelic acid weight (g)	Vanillic aldehyde theoretical amount (g)	Oxidation liquid weight (g)	Vanillic aldehyde content (%)	Vanillic aldehyde weight (g)
		1	101 102	775.2 776.6	7.28 7.29	56.43 56.61	43.32 43.46	1170.6 1186.4										3.61 3.48	42.25 41.29	97.53 95.00	2
2	103 104								780.0 767.8	7.23 7.36	56.39 56.51	43.29 4338	1170.3 1168.3	3.61 3.65	42.24 42.64	97.62 98.41	2.5
		3	105 106	769.1 768.7	7.28 7.34	55.99 56.42	42.98 43.31	1174.4 1172.3										3.57 3.60	41.93 42.20	97.56 97.44	2
4	107 108								778.3 779.2	7.41 7.18	57.67 55.95	44.27 42.95	1164.7 1169.7	3.70 3.59	43.09 41.99	97.33 97.76	2

Table 2 synthesizes the oxidation reaction result of Ethyl vanillin with oxidation catalyst of the present invention

Embodiment	The experiment lot number	Condensation liquid				Oxidation liquid			Oxidization-hydrogenation ratio (%)	Catalyst addition (g)
											Condensation liquid weight (g)	Ethyl mandelic acid content (%)	Ethyl mandelic acid weight (g)	Ethyl vanillin theoretical amount (g)	Oxidation liquid weight (g)	Ethyl vanillin content (%)	Ethyl vanillin weight (g)
		1	01 02	777.3 776.5	7.14 7.26	55.50 56.37	42.61 43.27	1177.9 1180.6										3.55 3.57	41.81 42.14	98.12 97.38	2
2	03 04 05								841.8 842.3 839.7	6.54 6.52 6.48	55.04 54.92 54.40	43.10 43.00 42.60	1174.4 1187.1 1168.5	3.58 3.57 3.55	42.02 42.38 41.48	97.54 98.56 97.37	2
		3	06 07	837.8 846.3	6.58 6.49	55.13 54.92	43.10 43.00	1182.4 1176.3										3.54 3.61	41.86 42.46	97.12 98.74	1.5
4	08								841.6	6.51	54.79	42.61	1191.2	3.47	41.33	97.02	1.5

Comparative example 1-2

Get the Na type catalyst and the 760g condensation liquid of the existing use of 2g oxidation catalyst of the present invention and 760g condensation liquid, 2g respectively, put into two Φ 80mm respectively, in the glass oxidizing tower of H1200mm, flow bubbling air in tower internal condensation liquid with 190 ± 10ml/h, in 93 ± 2 ℃ of reactions 7-8 hour, vanillic aldehyde content in the decarboxylation that heats up then, filtration, the analysis oxidation liquid.Discard filter cake, filtrate is pressed known method through extraction, distillation, recrystallization, makes vanillic aldehyde.Mandelic acid consumption, product oxidization-hydrogenation ratio etc. see Table each corresponding lot number of 3 interior comparative examples 1 and comparative example 2.

Comparative example 3-4

Get the Na type catalyst and the 830g condensation liquid (ethyl mandelic acid) of the existing use of 2g oxidation catalyst of the present invention and 830g condensation liquid, 2g respectively, put into two Φ 80mm respectively, in the glass oxidizing tower of H1200mm, flow bubbling air in tower internal condensation liquid with 190 ± 10ml/h, in 93 ± 2 ℃ of reactions 7-8 hour, the steps such as decarboxylation that heat up are then all undertaken by above-mentioned comparative example 1-2, make Ethyl vanillin.Ethyl mandelic acid consumption, product oxidization-hydrogenation ratio etc. see Table each corresponding lot number of 4 interior comparative examples 3 and comparative example 4.

The used raw material of the present invention, equipment can be purchased from the market.

Table 3 catalyst of the present invention _(※)With now use the Na catalyst _(Na)Be respectively applied for synthesis of vanillin result contrast

Comparative example	Lot number	Condensation liquid				Oxidation liquid			Oxidization-hydrogenation ratio (%)	Catalyst amount (g)
											Condensation liquid material heavy (g)	Mandelic acid content (%)	Mandelic acid weight (g)	Vanillic aldehyde theoretical amount (g)	Oxidation liquid weight (g)	Vanillic aldehyde content (%)	Vanillic aldehyde weight (g)
		1	1-1	760	7.08	53.808	41.307	1129.8										3.60	40.67	98.46	2 (※)
1-2	760								7.08	53.808	41.307	1117.8	2.78	31.07	75.21	2 (Na)
			2	2-1	760	7.08	53.808	41.307									1103.4	3.68	40.60	98.3	2 (※)
2-2	760	7.08							53.808	41.307	1110.4	2.86	31.76	76.88	2 (Na)

Table 4 catalyst of the present invention _(※)With now use Na type catalyst _(Na)Be used for synthesizing Ethyl vanillin result contrast respectively

Comparative example	Lot number	Condensation liquid				Oxidation liquid			Oxidization-hydrogenation ratio (%)	Catalyst amount (g)
											Condensation liquid material heavy (g)	Ethyl mandelic acid content (%)	Ethyl mandelic acid weight (g)	Ethyl vanillin theoretical amount (g)	Oxidation liquid weight (g)	Ethyl vanillin content (%)	Ethyl vanillin weight (g)
		3	1-1	830	8.06	66.89	52.376	1189.1										4.15	49.35	94.22	2 (※)
1-2	830								8.06	66.89	52.376	1197.1	3.89	46.57	88.91	2 (Na)
			4	2-1	830	8.06	66.89	52.376									1208.0	3.90	47.11	89.95	2 (※)
2-2	830	8.06							66.89	52.376	1190.8	3.81	45.37	86.62	2 (Na)

Claims (2)

1, the oxidation catalyst of the synthetic 4-hydroxy 3-methoxybenzene formaldehyde of a kind of acetaldehyde acid system and 4-hydroxyl-3-ethoxy-benzaldehyde in order to the element of this carbon monoxide-olefin polymeric of statement formation and the composition formula of molfraction thereof is:

(Mg) _a·(Mo) _b·(Fe) _c·(Cu) _d·(Zn) _e·(Al) _f·(K) _g·(Na) _h·O _x·S _y

In the formula, a, b, c, d, e, f, g, h, x and y are respectively the molfraction of Mg, Mo, Fe, Cu, Zn, Al, K, Na, O and S element, wherein,

The a value is that 0～0.3 b value is that 0～0.02 c value is 0.03～0.3

The d value is that 0.004～0.04 e value is that 0.002～0.07 f value is 0～0.7

The g value is that 0.009～0.4 h value is that 0～0.03 x value is 0.1～3

The y value is 0.05～0.9

This Preparation of catalysts method is as follows:

With the aluminium oxide of requirement or/and the iron oxide of requirement is raw material (I); The sulfate of getting required other metallic elements of the sodium salt of Mo element of requirement and requirement more respectively is raw material (II); Fully mix with raw material (I) with (II), add to ball milling 1h in the ball grinder then, make required oxidation catalyst.

2, oxidation catalyst according to claim 1 is characterized in that the molfraction of each element in this catalyst is respectively:

The a value is that 0.02～0.15 b value is that 0.003～0.015 c value is 0.04～0.25

The d value is that 0.006～0.035 e value is that 0.003～0.05 f value is 0～0.3

The g value is that 0.01～0.3 h value is that 0.006～0.02 x value is 0.20～2.5

The y value is 0.09～0.5.