AU609153B2 - Process for the hydrogenation of carbonaceous raw materials - Google Patents
Process for the hydrogenation of carbonaceous raw materials Download PDFInfo
- Publication number
- AU609153B2 AU609153B2 AU19096/88A AU1909688A AU609153B2 AU 609153 B2 AU609153 B2 AU 609153B2 AU 19096/88 A AU19096/88 A AU 19096/88A AU 1909688 A AU1909688 A AU 1909688A AU 609153 B2 AU609153 B2 AU 609153B2
- Authority
- AU
- Australia
- Prior art keywords
- cold
- slops
- hydrogenation
- process according
- stream
- 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.)
- Ceased
Links
- 238000000034 method Methods 0.000 title claims description 17
- 239000002994 raw material Substances 0.000 title claims description 13
- 238000005984 hydrogenation reaction Methods 0.000 title description 26
- 238000010438 heat treatment Methods 0.000 claims description 11
- 239000000243 solution Substances 0.000 claims description 11
- 239000003513 alkali Substances 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 239000007789 gas Substances 0.000 description 24
- 239000003921 oil Substances 0.000 description 11
- 239000011734 sodium Substances 0.000 description 11
- 229910052979 sodium sulfide Inorganic materials 0.000 description 8
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 239000000460 chlorine Substances 0.000 description 7
- 229910052801 chlorine Inorganic materials 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 239000003245 coal Substances 0.000 description 4
- 238000009833 condensation Methods 0.000 description 4
- 230000005494 condensation Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 235000019270 ammonium chloride Nutrition 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 235000017550 sodium carbonate Nutrition 0.000 description 2
- 150000003388 sodium compounds Chemical class 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000002144 chemical decomposition reaction Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000010742 number 1 fuel oil Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011269 tar Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
- C10G1/004—Inhibiting of corrosion
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Description
AUSTRALIA
Patents Act 609153 60 9 1 5 3 COMPLETE SPECIFICATION
(ORIGINAL)
Class Int. Class Application Number: Lodged:
A.
o 00o Ao A Complete Specification Lodged: Accepted: Published: Priority Related Art: o AC Ao 0
S.
AB A This document contains the amendments made under Section 49 and is correct for printing.
C.
1 APPLICANT'S REF.: P 37 25 367.0 Name(s) of Applicant(s): RUHRKOHLE AKTIENGESELLSCHAFT o 0 A A Address(es) of Applicant(s): Actual Inventor(s): Address for Service is: 4300 Essen, Federal Republic of Germany.
WOLOWSKI, ECKHARD PHILLIPS, ORMONDE AND FITZPATRICK Patent and Trade Mark Attorneys 367 Collins Street Melbourne, Australia, 3000 Complete Specification for the invention entitled: "PROCESS FOR THE HYDROGENATION OF CARBONACEOUS RAW MATERIALS" The following statement is a full description of this invention, including the best method of performing it known to applicant(s): P19/3/84 r PROCESS FOR THE HYDROGENATION OF CARBONACEOUS RAW MATERIALS The invention concerns the addition of alkali donors, particularly as sodium compounds, and of cold slops into the common high pressure circulation of a sump phase hydrogenation with integrated gas phase hydrogenation.
In the hydrogenation of carbonaceous raw materials, for instance coal, tars and high boiling oils, an alkali donor, especially as a sodium compound, is added to the raw materials in addition to a catalyst for the purpose of chemically binding chlorine in the raw materials which is then removed from the process together with the hydrogenation residue. Otherwise chlorine corrosion and salt formation (for example ammonium chloride) can occur in the condensation path of the oil products. In sump 2 phase hydrogenation with subsequent gas phase o hydrogenation, salt formation according to the equation
NH
3 HCl NH C1 (ammonium chloride) increases as the
NH
3 concentration in the circulating gas is increased because of the chemical decomposition of the nitrogen in the refined products.
In conventional hydrogenation, in particular o hydrogenation of coal, the sodium is added cs Na 2 S in solid form to the liquid carbonaceous raw materials. The S° Na S dissolves well in the crude oils which are rich in aromatics, especially raw coal oils from the sump phase hydrogenation. In refined inlet oils, ie oils low in aromatics, the solubility of Na2S is very low. Above :110°C the Na 2 S melts and upon further heating in the heating path, it gives up its water of hydration in stages. Recrystallysation of the Na 2 S can then occur in cooler zones and this can lead to blockages of pipelines, controls and containers.
Apart from Na S, soda-ash (Na 2
CO
3 is also used as an alkali donor. However, compared to Na 2
S,
soda-ash has disadvantages in that it has a specifically lower sodium content and its alkalinity is lower than that of Na2S. J 39 -2- Si)
AB
By means of feeding in alkali as aqueous Na2S S solution, the chlorine is bound and salt formation (ammonium chloride) in the gas heat exchangers is prevented.
Na 2 S in solid or molten form has poor solubility in refined solvents. Blockages then form in the initial mixing area. These difficulties do not occur if Na2S is added as aqueous solution into the heating path or into the sump path reactor.
In the operation of the sump phase hydrogenation with integrated gas phase hydrogenation, cold slops a a.
mixture of partially unrefined product oils and phenol containing water are also produced. The cold slops are do not as is otherwise usual in sump phase hydrogenation processed further by atmospheric distillation in which the ro refined oil products and possibly also the refined solvent o are separated as boiling fractions. This means that the cold slops, containing unrefined oils and phenol containing process water are not brought into contact with the refined oils during atmospheric distillation.
According to the present invention the cold slops are put 44*444 through the gas phase hydrogenation and refined.
SoThe present invention is based on feeding the alkali donor (preferably Na 2 S) into the high pressure 4,oo.4 S circulation while avoiding precipitation and blockage; and to continue to carry out cold slops processing without the use of an additional atmospheric distillation.
I 4 °o "According to the present invention there is provided .a process for the hydrogenation of carbonaceous raw material by sump phase hydrogenation with integrated gas phase hydrogenation, said process comprising: heating said raw material in the presence of a catalyst, with or without an additive, in a heating path to produce a heated pulp stream, feeding said pulp stream to a sump phase reactor, i feeding heated hydrogen containing gas to said reactor, carrying out sump phase hydrogenation of said 39 -3- BI RAI CuJ B llt1t i n pulp stream by said hydrogen containing gas in said reactor to produce products including gas phase products, ana feeding said gas phase products along a condensation path to a hot separator stage and an integrated gas phase hydrogenation stage; an alkali donor for binding chlorine in the raw material, and thereby substantially preventing chlorine corrosion and salt formation in said condensation path, being provided by feeding an aqueous solution of said donor to at least one of: 00 said heating path, eo (ii) said reactor, and (iii) said pulp stream prior to said reactor; 0090 cold slops being fed to at least one of; said heating path, s (ii) said reactor, (iii) said pulp stream prior to said reactor, and (iv) said condensation path, such that said cold slops are refined in said gas phase o hydrogenation stage.
#00990 0Th2 processing of cold slops in the sump phase 0009 o hydrogenation is solved according to the invention by Sofeeding the cold slops into the heating path or prior to 0000*0 the sump phase reactor or into the sump phase reactor.
It is preferred to feed cold slops and aqueous Na 2 S solution into the process together so as to save the need for additional high pressure pumps.
°If it is desired to feed the cold slops into the high pressure circulation separately from the Na2S solution, then cold slops are conveniently fed into the hot separator head product. In this matter the cold slops addition simultaneously supports temperature control in the gas phase reactor.
In FiiLre 1 is represented an embodiment of the present invention applied to coal hydrogenation with an integrated refining stage.
The feed mixture consisting of ground coal, 39 -4r~AB Vr U catalyst and oil is heated with a partial stream of the hydrogenation gas in the feed mixture heat exchangers (24,25) by indirect heat exchange with the hot separator head product stream and the gas phase product stream The greatest part of the hydrogenation gas consisting of circulating gas (15) and fresh hydrogen (17) is heated up as stream in the gas heat exchangers and in the furnace (30) and is added together with the preheated feed mixture to the sump phase reactor The aqueous Na2S solution is fed into the sump phase reactor either alone or together with the cold slops as stream (18) by means of the high pressure pump The heating and evaporation of aqueous Na2S 2 solution and cold slops in the sump phase reactor (31) results in the partial removal of the reaction heat and reduces, in this manner, the volume of quenching gas (16) needed for temperature control in the sump phase reactor.
The aqueous Na 2S solution can also be fed in together with the cold slops as a stream (i9) prior to the sump phase reactor (31) or as stream (20) between the feed mixture heat exchangers (24) and With cold slops CeoCt quantities which vary in time the furnace (30) is used to
.C.
Se. bring the reactor feed to a constant temperature.
Alternatively the cold slops alone or together oo with the vacuum gas oil are fed by means of high pressure pump (38) into hot separator head product stream *0 Variable heat transfer performances of the heat exchanger (25) can be compensated by varying the feed rate °of material stream (21) prior to, or of material stream (22) after, the feed mixture heat exchanger This facilitates a constant temperature control in the gas phase reactor (33).
The chlorine is bound to a great extent in the waste mud by the addition of aqueous Na S solution into 2 the process. The formation of salt in material stream and in gas heat exchanger (28) is thereby prevented.
In normal operation an injection of water to prevent salt formation is not necessary. The injection of VE water 39 AB RAl, vy AB
VTO-
L r, ~as i I (23) can be of use as a preventive measure after the intermediate separator into the material stream (12) if the dosage of the Na2S solution is not attuned to fluctuations of the chlorine content by tailing dependent on time. In addition the VE water injection aids the washing out of the ammonia in the circulation gas and this reacts favourably on the salt formation equilibrium in a suppressing direction. The separation of cold oil (13) and water (14) then takes place by means of differences of density in the cold separator (35) in the well known manner.
e r 4 t t e ft a a to ooaaoo a 39 -6a
I
a 7r~
Claims (6)
- 2. The process according to claim 1, wherein said aqueous solution of an alkali donor is aqueous Na 2 S solution.
- 3. The process according to claim 2, wherein said aqueous Na 2 S solution is fed into said heating path for said raw materials either separately from or together with said cold slops. 39 -7- W AB I.i r
- 4. The process according to claim 2, wherein said aqueous Na 2 S solution is fed into said sump phase reactor, or into said heated pulp stream prior to said sump phase reactor, either separately from or together with said cold slops. The process according to claim 1 or 2, wherein said heating path includes a heat exchanger, which functions to exchange heat from said stream of said gas products to said raw materials and thereby heats said raw materials.
- 6. The process according to claim 5, wherein said cold slops are fed into said stream of said gas products prior to said heat exchanger either alone or together with a" vacuum gas oil. *o o
- 7. The process according to claim 5, wherein said cold S slops are fed into said stream of said gas products after ao, 4, said heat exchanger either alone or together with vacuum gas oil.
- 8. The process according to claim 1, substantially as herein described with reference to the accompanying drawing. 17 JANUARY, 1991 PHILLIPS ORMONDE FITZPATRICK S Attorneys For: RUHRKOHLE AG i 20753 39 -8- t^h M XP 0I B 'Vr -o
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3725367A DE3725367C1 (en) | 1987-07-31 | 1987-07-31 | Process for the hydrogenation of carbonaceous feedstocks |
| DE3725367 | 1987-07-31 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| AU1909688A AU1909688A (en) | 1989-02-02 |
| AU609153B2 true AU609153B2 (en) | 1991-04-26 |
Family
ID=6332766
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| AU19096/88A Ceased AU609153B2 (en) | 1987-07-31 | 1988-07-15 | Process for the hydrogenation of carbonaceous raw materials |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP0301172B1 (en) |
| JP (1) | JPS6436686A (en) |
| AU (1) | AU609153B2 (en) |
| BR (1) | BR8803775A (en) |
| DE (2) | DE3725367C1 (en) |
| PL (1) | PL151645B1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7678163B2 (en) | 2005-04-29 | 2010-03-16 | Scf Technologies A/S | Method and apparatus for converting organic material |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2606762C (en) | 2005-04-29 | 2014-10-14 | Scf Technologies A/S | Method and apparatus for converting organic material |
| WO2007059783A1 (en) * | 2005-11-24 | 2007-05-31 | Scf Technologies A/S | Method and apparatus for converting organic material using microwave excitation |
| CN104388118B (en) * | 2014-11-24 | 2017-01-04 | 湖南省馨盛能源开发有限责任公司 | The technological process of producing diesel by coal tar |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE692631C (en) * | 1934-09-26 | 1940-06-24 | I G Farbenindustrie Akt Ges | Process for preventing corrosion in the heat treatment of coal, tars, mineral oils and the like like |
| US4388172A (en) * | 1980-10-10 | 1983-06-14 | Ruhrkohle Aktiengesellschaft | Liquefaction of coal |
-
1987
- 1987-07-31 DE DE3725367A patent/DE3725367C1/en not_active Expired
-
1988
- 1988-04-12 DE DE8888105773T patent/DE3861308D1/en not_active Expired - Lifetime
- 1988-04-12 EP EP88105773A patent/EP0301172B1/en not_active Expired - Lifetime
- 1988-07-14 JP JP63173851A patent/JPS6436686A/en active Pending
- 1988-07-15 AU AU19096/88A patent/AU609153B2/en not_active Ceased
- 1988-07-21 PL PL1988273853A patent/PL151645B1/en unknown
- 1988-07-29 BR BR8803775A patent/BR8803775A/en unknown
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE692631C (en) * | 1934-09-26 | 1940-06-24 | I G Farbenindustrie Akt Ges | Process for preventing corrosion in the heat treatment of coal, tars, mineral oils and the like like |
| US4388172A (en) * | 1980-10-10 | 1983-06-14 | Ruhrkohle Aktiengesellschaft | Liquefaction of coal |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7678163B2 (en) | 2005-04-29 | 2010-03-16 | Scf Technologies A/S | Method and apparatus for converting organic material |
Also Published As
| Publication number | Publication date |
|---|---|
| DE3725367C1 (en) | 1988-09-22 |
| PL151645B1 (en) | 1990-09-28 |
| EP0301172A3 (en) | 1989-07-26 |
| EP0301172B1 (en) | 1990-12-19 |
| EP0301172A2 (en) | 1989-02-01 |
| PL273853A1 (en) | 1989-04-03 |
| BR8803775A (en) | 1989-02-21 |
| AU1909688A (en) | 1989-02-02 |
| JPS6436686A (en) | 1989-02-07 |
| DE3861308D1 (en) | 1991-01-31 |
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