FI125561B - Hydrogen treatment of crude tall oil to produce aromatic monomers - Google Patents

Description

The crude tall oil hydrotreating to produce aromatic monomers

The invention relates to a method for treatment of the crude tall oil with hydrogen to produce aromatic monomers.

Aromatic monomers, production of traditional raw material has formed a petroleum. Aromaattijakeita obtained in the fractional distillation of petroleum is further processed aromatic monomers, substituted or unsubstituted, such as benzene, xylene and phenol to obtain. With N aromaattijakeiden, starting material is recovered alifaattijakeita also be used for example. polymers as raw materials.

A viable alternative to fossil raw materials in the manufacture of polymers have been sought from renewable organic raw material sources. Polymers have been shown to be manufactured mm. maize or sugar, however, the drawback is that the po-lymeerituotanto will then contest the same raw materials with food production, whose resources are limited on a global scale. Among these sources, by-stream cyclic aromatic compounds are also collected for special applications. The ideal source of raw material would form a tree whose reserves are abundant and where there is no use for food production.

US-2004/0 230 085 is known as a catalytic hydrodeoksygenointi tall oil fatty acids as part of the production of bio-based diesel fuel. Deoksy-genointi takes place with hydrogen gas in the catalyst bed, which is metallikatalyyt-acetate, NiMo or a CoMo like, and the applicant alumina and / or silica. Deoksygenointivai generated at stage a gas mixture is separated from the carbon oxides and various impurities, and the purified hydrogen is recycled back to the process. Liquid phase is carried out in the second stage of the process isomerization, which changes the product suitable for fuel use. Since the isomerization step is delicate and nafteeniepä-aromatic impurities, the starting material is removed as much as possible of tall oil resin acids, which are deoksygenoinnissa can be formed. Example 1 publication resin was 1.9% among the fatty acids.

US-2008/0 154 073 a similar process for producing diesel fuel from renewable bio-based materials, such as vegetable oils is shown. As a potential raw material mentioned tall oil fatty acid with addition of resin acids, but the test results of the tall oil produced a significant portion of the die-ble heavier hydrocarbon fractions, as opposed to soy oil is also used in the experiments.

Also in US-2007/0 135 669 describes the production of diesel fuel from renewable bio-based raw materials and remarking of unsaturated and aromatic hydrocarbons, non-desirability of the final product. The publication discloses an invention of the process, where the distilled tall oil fatty acids are first isomerized and then the next step of the process deoksygenoidaan.

WO-2009/004 181 A2 discloses a catalytic vegetable oils, hydrocracked stability and the subsequent steam cracking polymerointikelpoisiksi monomers. The publication mentioned vegetable oils do not contain tall oil resin acids.

Publication US 5705722 A discloses a tall oil fatty acids and resin mixture to a catalytic hydrocracking, and previous use of the product as additives in diesel fuel. The publication does not disclose the recovery of aromatics.

The purpose of the present invention is to provide an industrially useful process in which the wood-based raw material is converted into a value of the processing monoaromaateiksi interesting. Preparation of such aromatics based on renewable biological raw material sources. The method according to the invention consists essentially of hydrogen gas and a bio-oil with 2-90% tall oil fatty acids, and 2-98% tall oil resin acids, is fed to the catalytic bed, with a NiMo catalyst, oil deoksygenoidaan the bed with hydrogen in the catalytic leaving the bed stream is cooled and divided hydrocarbonaceous liquid-phase and gas phase, aromatics hydrocarbonaceous liquid phase is recovered, and optionally steam cracking of hydrocarbonaceous liquid is performed acid-polymerizable olefin-containing product.

The present inventors have surprisingly found that when using the method of the catalyst, which is a NiMo catalyst or optionally katalyyttiyhdistel-group, with a NiMo catalyst and ZSM-5 catalyst may be tall oil (Crude talloil, CTO), and a bit fractionated mäntyöljytisleellä (Distilled talloil DTO) and the system työljyjen fatty acids (tall oil fatty acid, TOFA), the hydrogen in the form monoaromaatteja BTX (benzene, toluene, xylene), which are separable and further useful for the preparation of aromatic chemicals.

Unexpected advantage, the inventors also found that these catalysts (NiMo, ZSM-5, and combinations thereof) there is no build-up or polycyclic catalyst. Thus, they were less expensive than acidic motmoroliitti used as one of a catalyst, which messes up the process.

The oil starting material may be pure tall oil fatty acids based consisting of pine oil and at least 2%, preferably at least 25% of tall oil rosin acid and. The crude tall oil composition corresponding to these values, but the preferred acid mixtures can be separated from the crude tall oil distillation.

The end product of the process of the invention obtained from aromatic monomers can be changed exclusively on renewable raw material source-based, conversion.

It is also possible to blend the starting material of pine oil Components other suitable bio-oil such as vegetable oils, e.g. palm oil.

Pine oil (tall oil) refers to the invention not only made of pine (Pinus), as well as other conifers available, consisting of a fatty and resin acids or esters of oil products.

The invention is based on the fact that tall oil fatty acids per se carried out in a known manner hydrodeoksygenointi produce a liquid product, hydrocarbon mixture, which can be further processed aromatic chemicals (benzene, toluene, and other mono-, di- or tri-alkylbenzenes, and the heteroatom of O, N, S, include one-ring benzene derivatives) producing the same. When the aromatics separation and processing is normal within the petrochemical technology, is the implementation of the process according to the invention in practice easy.

The process according to the invention is the presence of the said components less sensitive to the manufacture of diesel fuel, excluding tall oil rosin acids to be separated from one specific fatty acids. The inventors have found that even hartsihap-acids share at least 25% of the starting material, the process can be carried out smoothly and aromatics from derivatives recovered for further use. Aliphatic downstream of the fractions takes place according to the applicant's as yet unpublished patent application, the method of FI20095079 instance, the höyrykrakkerilla.

Hydrodeoksygenointi catalytic effect on fatty acids by removing the oxygen and formation of water, carbon monoxide and / or carbon dioxide. Significant breakage of the carbon chains into smaller molecules do not yet take place, which is the preferred aromatic-en collected by acquiring. In the invention, use of the catalytic fixed bed may be limited deoksygenointivaiheeseen.

An alternative embodiment of the invention is that of the deoksygenointia Kiin-topedissä catalytic cracking to lower molecular weight, wherein the deoksy-genointi- and cracking catalysts are different from each other. Cracking generates unsaturated hydrocarbons and releases hydrogen so that those leaving ve typitoinen gas, it is preferable to recycle back to deoksygenointivaiheeseen. In this case, it is even possible that the process requires an external source of hydrogen only the start-up phase and works after only depend on the recycled hydrogen.

Fixed bed occur cracking catalyst can be used acidic catalysts such as zeolite or an acidic montmorolliittikatalyyttiä. Deoksy-genointivaiheen catalyst, regardless of any catalytic cracking, NiMo catalyst is used. The catalyst is known as hydrogen reduced and treated with hydrogen sulfide. In the method according to the invention NiMo catalyst is preferred because it produces a CTO feed aromatics in a high yield, but is not sensitive to coking.

Suitable catalysts hydrodeoksygenointi and a major catalyst to crack-in can take place in the bed at the same time. Such catalysts are nickel-containing Y-zeolite (YIC-zeolite) or nickel-containing montmoroliitti (NiSMM), which require a high hydrogen pressure in the reactor. NiSMM krakkaa also resin acids, and is therefore particularly advantageous for the efficient use of tall oil components for.

A suitable reaction temperature hydrodeoksygenointivaiheessa and possible catalytic cracking is between 330-450 ° C. At lower temperatures the risk of polymerization, coking at higher temperatures, the fatty acids in the feed to the reactor. In order to avoid coking preferred temperature is between 330-400 ° C.

The invention also comprises the fact that bio-oil is combined with petroleum sub-streams are processed, resulting in the final part of the polymerization are respectively

The invention also comprises the fact that bio-oil is combined with petroleum sub-streams are processed, resulting in the final part of the polymerization are respectively bioperustainen and into the petroleum-based hybride. The bio-oil and petroleum mixture ratio according to the invention hydrodeoksygenointi- and the cracking process is freely selectable in a while.

The invention is described initially in referring to the accompanying drawing (Fig.1), which shows schematically an apparatus suited for implementing the invention.

Bio-oil according to the drawing, such as tall oil fatty acids hydrodeoksygenointi- and cracking of the basic steps of the vertical reactor is one place in the catalytic deoksygenointi and cracking 2, 3, and from these stages of liquid hydrocarbons (olefins 14, and aromatics A) downstream separate apparatus 4, which corresponds to the petrochemical industry technique known per se. Separated by distillation of tall oil fatty acids, which may be accompanied by up to 25% resin acids, feed 5 takes place in reactor 1 at the upper end. In addition, the upper end of the reactor 1 is brought into line 6. Reactor hydrogen-7-petimate a working material for 1 filled with quartz wool, which overlapping, spaced apart zones 2, 3 is a NiMo catalyst and zeolite deoksygenoimiseksi supplied montmorilloniittikatalyyttiä acids or cracking of the carbon chain. The liquid and gas-phase reactor, one flow direction is from the top down. For controlling reaction temperatures in the reactor 1 is equipped with an electric heater 8.

Reactor 1 at the lower end removed from the hot reaction products into the radiator 9, and the liquefied product is transferred via line 10 to a separation tank 11, which is separated from the aqueous phase 12 from the oil phase 13. The oil phase 13, whose main component is typically a saturated aliphatic hydrocarbons, and which may also have varying amounts of cyclic and aromatic hydrocarbons, unsaturated hydrocarbons, fatty alcohols, transferred to further processing to 4, wherein A aromatics are recovered and are further processed according to the prior art processes in which low molecular weight olefins and 14 can be steam-cracking. Olefins used as biopolymers, such as polyethylene or polypropylene as starting materials. Aromatics used in the production of bio-based chemicals.

The cooler 9 tiivistymättä residual gas containing hydrogen, carbon oxides, optionally low molecular weight hydrocarbons and other pollutants, and moves the cleaner 15 which separates hydrogen from other gas components. Pure hydrogen is recycled via line 16 back to reactor 1 at the upper end deoksygenointikaasuksi, and carbon oxides et al. Contaminants 17 are removed from the process.

Process according to the alternative embodiment of the invention, is that the zeolite catalyst reactor 1 is replaced by three montmorilloniittikatalyytilla. The remainder of the apparatus and process flow are as shown in the drawing.

Examples

Example Experiments 1-6, comprising hydrodeoksygenoinnin (HDO) and / or catalytic cracking (CC), performed in a batch principle of the flow-through reactor without recycling of the gas phase. The numbers listed below refer to the ranges of the differences between the parameters of the tests. Liquid and gas phases obtained from the reactor were analyzed. The process of the invention, the following organic liquid phase steam-cracking was not performed, since it is well known to those skilled in the art and suitability for steam cracking in a liquid, the analyzes were evident.

Electric furnace within the vertical reactor tube was packed zeolite catalyst (ZSM-5) and the nickel-molybdeenikatalyyttiä (NiMo, alumina) montmorilloniittikatalyyttiä or any combination thereof. The amount of each catalyst are shown in grams talulukossa 1 through the packed catalyst NiMo catalysts esisulfidoitiin reactor tube by passing a hydrogen sulphide-containing stream of hydrogen 393 ° C temperature for five hours.

The reactor tube temperature was adjusted depending on the experiment 360-450 ° C and purged with hydrogen gas at a pressure of 31-32 bar from the top downwards. Vetyvirraksi the reactor was set at about 1 g / h, range from 0.87 to 1.40 g / hr. When the flows and temperatures had stabilized reactor tube started to pump in addition to the hydrogen-mäntyöljytis distillate containing free fatty acids, in addition to a little resin. There were also the unsaponifiable fraction. The acid number varied from the lowest 174 to <200. Mäntyöljytisleen pass took place from the top of the reactor tube, downstream of the hydrogen flow. Mäntyöljytisleen feed rate was adjusted to 6.0 to 8.3 g / h. Catalysts in terms of WHSV (Weight Hourly Space Velocity) ranging from 2.0-2.3, therefore, h'1 HDO catalyst and 2.0-6.0 h'1 CC-catalyst, respectively ..

Coming out of the reactor, the lower end of the liquid / gas flow is introduced into the pressurized collection vessel, cooled with cold water. Keruuastiasta were collected throughout the nestesiältö collected every hour. Keruuastiasta exiting gas stream passed through the pai-relief valve in the open air. The gas exposure was measured on-line analyzer composition of each hour and the reactor was run a total of 10 hours.

Eight hours driving time into the reactor was entirely balanced, was recovered in 83% of the liquid product supplied mäntyöljytisleen väähintään. The liquid product was organic phase and the separated water. The liquid product had a total of hydrocarbons ranging from 50-73% of the volume of the organic phase in the low RDF feed of NiMo / ZSM-5 catalyst and the feed of a maximum of TOFA-NiMo-catalyst. The organic phase approximate compositions varied considerably and they can read the table with regard to one of the following components: aromatic hydrocarbons, saturated hydrocarbons, unsaturated aliphatic hydrocarbons and fatty alcohols in total and cyclic hydrocarbons. The reactor in the gas stream exiting the reaction products of 2-17%, depending on the experiment the amount of supplied mäntyöljytisleen, the smallest return gas comes up to TOFA feed of n-i-katal MO yl 11a and most of RDF feed of NiMo / ZSM-5 catalyst. The gas flow, the reaction products were: carbon monoxide, carbon dioxide, C1 and C2, total hydrocarbons, C3 hydrocarbons and C4 hydrocarbons, and proportions of heavier hydrocarbons, which can be read in table 1.

The test measured the mass balance was closed quite well. Measured out the mass flows were a total of at least 84%, the highest 97% of RDF feed of NiMo / ZSM-5 -yhdistelmäkatalyytilla all entered the reactor flows.

Tests 1-6 the results are in the following table. Tests 1, 3 and 5 feed of tall oil, distilled fatty acids response (TOFA), wherein the resin acids of about 2%, the test four of distilled tall oil (DTO), which resin was about 25-30%, and in Experiments 2 and 6 of the crude tall oil (CTO), where resin was approximately 25%.

Catalysts are shown hydrodeoksygenointivaiheen (HDO), and a catalytic krak-cutting phase (CC) separately.

Test the low proportion of saturated hydrocarbons 4 shows too advanced cracking and thus the relevance of the HDO step. Experiments 5 and 6 show the starting material resin acids to increase the proportion of aromatics in Test 6 of adverse high.

Table 1

Claims (12)

A process for producing monoaromatics, such as benzene, toluene or xylene, characterized by the following steps: a. 7), containing a NiMo catalyst, b. - the oil is catalytically dehydrogenated in the bed (7) with hydrogen, c. d. The monoaromatics (A) formed in the hydrogen treatment are separated from the hydrocarbon-containing liquid phase. The method of claim 1, further comprising a step in which steam cracking is selectively performed by the hydrocarbon-containing liquid to form a product containing polymerized olefins. The method of claim 1, wherein said bio-oil is tall oil based, comprising at least 25% tall oil based resin acids. The process according to claim 1, wherein said bio-oil has been separated from the crude oil by distillation. A method according to any one of the preceding claims, wherein the catalyst bed is a fixed bed (7) consisting of solid bed material. 6. Process according to claim 5, characterized in that the cracking chain catalyst is acidic, such as an acidic zeolite catalyst, advantageously a ZSM-5 catalyst. Process according to claim 5 or 6, characterized in that the catalysts of the deoxygenation and cracking steps (2, 3) are successively separated from each other in the fixed bed (7) consisting of bed material. Method according to one of the preceding claims, characterized in that the flows in the bed (7) occur from the top downwards. 9. A process according to any one of the preceding claims, characterized in that the hydrogen-containing gas phase (16) separated from the liquid phase (10) is recirculated as feed gas for the deoxygenation step (2). Process according to one of the preceding claims, characterized in that water (12) is separated from the liquid phase (10) before the hydrocarbon-containing liquid (13) is fed to further processing (4). 11. A process according to any one of the preceding claims, characterized in that the hydrocarbon-containing liquid phase (10, 13) contains hydrocarbons within the boiling range of diesel oil. Process according to claim 2, characterized in that olefin (14) containing ethylene and / or propylene is produced by the refining (4).