PLANT AND PROCESS FOR PRODUCING PURIFIED METHANOL

Abstract

The present invention relates to a plant for removing C.sub.6-C.sub.11 hydrocarbons from methanol, comprising at least one reactor for the conversion of carbon monoxide and hydrogen to a crude methanol containing hydrocarbons, a distillation column with a head and a sump for the purification of the methanol, and at least one conduit for guiding the crude methanol from the at least one reactor into the distillation column. At its head, the distillation column includes a feed conduit for feeding in water.

Claims

1-15. (canceled)

16. A plant for removing C.sub.6-C.sub.11 hydrocarbons from methanol, comprising: at least one reactor for the conversion of carbon monoxide and hydrogen to a crude methanol containing hydrocarbons, a distillation column with a head and a sump configured to purify the methanol, and at least one conduit configured to guide the crude methanol from the at least one reactor into the distillation column, wherein the head of the distillation column includes a feed conduit configured to feed in water to the head of the distillation column.

17. The apparatus according to claim 16, wherein in the at least one conduit for the supply of the crude methanol from the reactor into the distillation column at least one flash evaporator is provided for separating gases from the crude methanol.

18. The apparatus according to claim 17, wherein downstream of the at least one flash evaporator at least one scrubber is provided such that in the at least one scrubber the separated gases are purified by means of a water wash.

19. The apparatus according to claim 18, wherein the feed conduit is designed such that it guides the washing water from the at least one scrubber into the head of the distillation column.

20. The apparatus according to claim 16, wherein the distillation column is designed such that the purified methanol is withdrawn via the sump.

21. The apparatus according to claim 16, wherein in its head the distillation column includes a reflux device with a heater and a condenser and the feed conduit opens into the reflux device.

22. The apparatus according to claim 16, wherein the distillation column is a packed column or contains sieve trays or bubble trays.

23. A process for removing C.sub.6-C.sub.11 hydrocarbons from methanol, the process comprising the steps of: converting carbon monoxide and hydrogen to a crude methanol containing hydrocarbon; and purifying the crude methanol in a distillation column with a head and a sump, wherein water is added to the head of the column during purification of the crude methanol.

24. The process according to claim 23, wherein 1 to 15% of water based on the total volume flow of inflow and water fed in is added.

25. The process according to claim 23, wherein the contained hydrocarbons contain six to eleven carbon atoms in an amount of at least 50%, preferably 80%, based on the total volume flow of all contained carbon atoms.

26. The process according to claim 23, wherein the crude methanol contains between 90 and 97 vol-% of methanol, between 3 and 10 vol-% of water, up to 0.5 wt-% of hydrocarbons with an amount of C.sub.9+ fraction of up to 15%, and 0.3 vol-% of further impurities.

27. The process according to claim 23, wherein the distillation column includes a reflux.

28. The process according to claim 27, wherein the reflux ratio lies between 1 and 5.

29. The process according to claim 23, wherein the distillation column is operated at a temperature between 75 and 100° C. and/or at a pressure of 1 to 3 bar.

30. The process according to claim 23, wherein a flux withdrawn over head corresponds to 0.3 to 0.7 vol-% of the inflow into the distillation column.

Description

[0034] Further developments, advantages and possible applications of the invention can also be taken from the following description of the drawing and the exemplary embodiments. All features described and/or illustrated form the subject-matter of the invention per se or in any combination, independent of their inclusion in the claims or their back-references.

[0035] In the drawing:

[0036] FIG. 1 shows a plant according to the invention for removing C.sub.6-C.sub.11 hydrocarbons from methanol with a column designed according to the invention.

[0037] FIG. 1 shows the flow diagram of a plant or a process for removing C.sub.6-C.sub.11 hydrocarbons from methanol. In the process, the educts carbon monoxide and hydrogen are introduced into a reactor 4 via conduit 1 and valve 2 as well as conduit 3.

[0038] From the reactor 4, methanol synthesized already together with non-converted educts can be introduced via conduit 5 into a downstream reactor 7, from which the crude methanol obtained together with non-converted educts is recirculated via conduit 6 into the reactor 4, in which it acts as heating medium for the reaction taking place there and is cooled at the same time.

[0039] The crude methanol along with remaining, non-converted educts then is withdrawn via conduit 8 and supplied to a high-pressure flash evaporator 11. This high-pressure flash evaporator 11 is operated at 60 to 100 bar. Gaseous components are supplied to the valve 13 via conduit 12. Via conduit 14, parts of the gaseous components are recirculated into the valve 2 by means of a non-illustrated condenser and from there are introduced into the reactor 4 via conduit 3, in order to ensure that still contained carbon monoxide and hydrogen can be converted in the reactor to obtain a valuable product.

[0040] Via conduit 15, the remaining rest is supplied to a scrubber 16. This this scrubber 16, washing water is supplied via conduit 17. Via conduit 18 the purified gas is discharged, while the washing water is passed on via conduit 19.

[0041] Liquid constituents are discharged from the high-pressure flash evaporator 11 via conduit 20 into a low-pressure flash evaporator 21, which is operated at 1 to 3 bar absolute. From the low-pressure evaporator 21 further gases are supplied to a scrubber 23 via conduit 22. Conduit 19 opens into the scrubber 23, which thus supplies the washing water to the scrubber 23. Via conduit 24, the purified gases are withdrawn. It is, however, also conceivable to supply the two scrubbers 16 and 23 with separate streams of washing water, in order to avoid an entrainment of impurities.

[0042] Via conduit 25, the purified liquid fractions are supplied to a distillation column 30. Its bottom product is withdrawn via conduit 31 and substantially consists of methanol. Via conduit 32, the top product is supplied to a heater and heated there. The correspondingly heated product is passed into the condenser 36 via conduit 34. Liquid constituents are recirculated into the distillation column 30 via conduit 37, while via conduit 38 gaseous products are supplied to the second heater 39 from which they are withdrawn via conduit 40.

[0043] Via conduit 42, water can be recirculated from the scrubber 23 into the flash evaporator 21.

[0044] According to the invention, a feed conduit 41 leads from the scrubber 23 into the condenser 36 and here introduces the liquid water. In the same way, however, the water stream also can be withdrawn already from the scrubber 16, or a separate water stream or a water stream obtained at another point in the process can be fed in. It likewise is conceivable to provide a separate supply for the water at the head of the column or to already charge the water into the heater 33 and thus bring it up to temperature.

[0045] By this addition of water, hydrocarbons with a chain length of six to eleven carbon atoms can be separated effectively.

EXAMPLES

Example 1

[0046] The example shows the comparison between a conventionally operated distillation column and one operated according to the invention. As shown in Table 1, the content of hydrocarbons with a chain length between six and eleven carbon atoms decreases significantly. In the first experiment, a total of 2000 wt-ppm of hydrocarbons (HC) were charged to the feed and in the second experiment a total of 1000 ppm each with 15 vol-% of C.sub.9+ fractions. In the first experiment, a HC concentration of 240 ppm could be detected in the sump, in the second experiment still 60 ppm. It could be demonstrated that the hydrocarbons in the sump exclusively consist of a C.sub.9+ fraction. The low-boiling components were separated over head. Thus, the separation efficiency with head injection could be increased to 30% recovery based on the C.sub.9+ fraction of 80%. In particular, hydrocarbons with 10 C-atoms could be separated significantly better.

TABLE-US-00001 TABLE 1 Conditions of the two runs carried out according to Example 1 Experiment 1 Experiment 2 Inflow (g/h) 400 400  Water addition at the head (g/h) — 12 Water content (% of the inflow) 5  3* Reflux rate 20 20 Head flux (% of the inflow) 6  6 Pressure/bar 2.3   2.3 Hydrocarbons in the feed (ppm (mass)) 2000 1000  C.sub.9+ fraction of hydrocarbons/% 15 15 Recovery** hydrocarbons/% 12  6 Hydrocarbons fraction in the sump/ppm 240 60 (mass) C.sub.9+ fraction/ppm (mass) 100 100  Recovery** C.sub.9+/% 80 30 *with water added over head also 5% of the inflow. **Recovery = mass of the component in the sump/mass of the component in the feed

Example 2

[0047] Crude methanol from a plant with pure quality, i.e. high hydrocarbon concentrations, was charged to a distillation column at a height of four meters, with an inner diameter of 50 mm and 20 separation stages. The methanol was introduced continuously at the separation tray 15. The reflux at the head of the column was adjusted such that it was 2% of the methanol inflow.

[0048] At first, no water was added (Experiments 1 and 2). By addition 10 vol-% of water to the inflow, the quality of the separated methanol could be increased already (Experiments 3 and 4). By adding such an amount of water at the head of the column that it was 0.56% of the methanol inflow, the specifications of the turbidity test according to Spec O-M-232L could be met (Experiments 5 to 8).

TABLE-US-00002 TABLE 2 Experimental conditions with continuous forerun distillation Experiment No. 1 2 3 4 5 6 7 8 Addition of water to crude methanol — — 10 10 — — — — (vol-%) Addition of water at the head (g/h) — — — — 10 10 10 10 Feed quantity of crude methanol (1/h) 3.0 2.0 2.7 2.7 2.7 2.7 2.7 2.7 Feed quantity of water (1/h) — — 0.3 0.3 0.3 0.3 0.3 0.3 Top product of the total feed (%) 2 5 2 2 2 1 1 0.5 Top product of the crude methanol (%) 2 5 2.2 2.2 2.2 1.1 1.1 0.56 Boiling rate (W/h) 100 100 100 133 133 133 133 133 Dissipated condensation heat (kcal/h) 77 77 77 77 77 77 77 77

[0049] For determining the purity, the turbidity of the methanol was measured as significant quantity on a scale from 0 (complete impermeability to light) to 100 (completely clear). The prepurified methanol then was distilled again in a further column for water separation, wherein the above-mentioned volume fraction each was withdrawn over head as pure methanol.

[0050] Without addition of water (Experiment 1) hydrocarbons still are found in all fractions, independent of how clearly the separation is made in this downstream column, as here turbidities occur. By addition of water in Experiments 2 and 3 into the inflow, the turbidities could be reduced distinctly. When water is added over head (Experiments 5 to 8), the hydrocarbons obviously are separated even better and a reduction of the top product withdrawn is achieved, as is shown by the reduced turbidity.

TABLE-US-00003 TABLE 2 Turbidity values of the fractions from the discontinuous laboratory distillation; there was each used stabilized methanol from a continuous distillation Fraction 70- Total 0-10% 10-20% 20-30% 40-50% 80% distillate* Experiment 1 <50 72 83 94 — — Experiment 3 76 92 97 98 96 94 Experiment 4 80 95 98 99 99 96 Experiment 5 98 100 100 98 98 98 Experiment 6 99 100 96 99 100  99 Experiment 8 99 100 100 100 — 100  *Distillation here was carried out until the head temperature had increased by 0.2-0.3° C. above the value constant during the preceding time. This practically corresponds to a complete distillation of the sump.

TABLE-US-00004 TABLE 3 Pure-methanol analyses from Experiments 9 and 10 as compared to a reference. Experiment 9 (from Experiment 10 Experiment (from Crude 7) Experiment 8) Reference MeOH Density 0.792 0.792 0.792 Water (ppm) 220 250 200-500 Boiling interval 0.45 0.2 0.35 (° C.) Acid (ppm) 15 15 15 Permanganate 75 70 35-45 index (min) Gas chromatography Acetone 19 11 13-22 51 Methyl formate 150 135 120 606 Ethanol 380 290 n.a. 698 Unknown** 980 1000 1040 885 *A still unknown, presumably higher-boiling substance coincides with methyl formate. **These are 5 components, two of which constitute the main fraction. Experiment 9 relates to Distillation Experiment No. 7 and Experiment 10 relates to No. 8

REFERENCE NUMERALS

[0051] 1 conduit [0052] 2 valve [0053] 3 conduit [0054] 4 reactor [0055] 5, 6 conduit [0056] 7 reactor [0057] 8 conduit [0058] 11 flash evaporator [0059] 12 conduit [0060] 13 valve [0061] 14, 15 conduit [0062] 16 scrubber [0063] 17-20 conduit [0064] 21 flash evaporator [0065] 22 conduit [0066] 23 scrubber [0067] 24, 25 conduit [0068] 30 distillation column [0069] 30a sump (of the distillation column) [0070] 30b head (of the distillation column) [0071] 31, 32 conduit [0072] 33 heater [0073] 34 conduit [0074] 36 condenser [0075] 37, 38 conduit [0076] 39 heater [0077] 40 conduit [0078] 41 feed conduit [0079] 42 conduit